TiAl合金表面搪瓷基复合涂层与多弧离子镀NiCrAlY涂层的抗热腐蚀行为对比研究

以Ti-45Al-2Mn-2Nb合金为基体,采用多弧离子镀制备NiCrAlY涂层、喷涂-烧结法制备搪瓷基复合涂层,对比研究了2种涂层以及合金基体的热腐蚀行为。热腐蚀实验温度为850℃,选用饱和盐溶液溶质成分为75%Na_2SO_4+25%NaCl (质量分数),涂盐量为1.5～2.5 mg/cm~2。研究结果表明,合金基体完全不具备抗热腐蚀能力,表面形成的氧化膜疏松多孔,且极易剥落;NiCrAlY涂层表面生成的保护性Al_2O_3膜提高了合金的抗热腐蚀能力,然而涂层与基体间严重的互扩散及Al_2O_3膜与熔盐的碱性溶解使得NiCrAlY涂层逐渐失效,热腐蚀60 h即出现氧化膜的剥落;而搪瓷基复合涂层在熔盐环境中只发生了轻微的物理溶解,具有极高的热稳定性及较低的热腐蚀速率,有效地阻隔了腐蚀性离子的入侵,抗热腐蚀性能优异。     

NiCrAIY涂层对Ni基高温合金K17抗氧化性能的影响

采用电弧离子镀技术在铸造Ni基高温合金K17上沉积NiCrAlY涂层,测定了K17合金和NiCrAlY涂层在900℃～1100℃的氧化动力学曲线.实验结果表明:K17合金和NiCrAlY涂层在不同温度静态空气中氧化动力学曲线基本符合抛物线规律.900℃和1000℃时,K17合金上沉积NiCrAlY涂层后,明显改善了合金的抗氧化性.1100℃时,涂层的保护作用不如900℃和1000℃.900℃氧化时,NiCrAlY涂层氧化膜由α-A12O3和Cr2O3组成;1000℃氧化时,氧化初期,NiO、Cr2O3和A12O3 3种氧化物同时生成.随着氧化的进行,不仅氧化膜增厚,而且发生较复杂的反应,氧化膜的相组成发生变化.随着氧化温度升高,涂层和基体之间元素扩散加剧,Ti从基体扩散到涂层表面形成氧化物是导致涂层抗氧化性降低的原因之一.氧化膜从涂层上剥落下来,也导致了涂层抗氧化能力降低.     

NiCrAlY涂层对Ni基高温合金K17抗氧化性能的影响

采用电弧离子镀技术在铸造Ni基高温合金K17上沉积NiCrA1Y涂层，测定了K17合金和NiCrAlY涂层在900℃-1100℃的氧化动力学曲线。实验结果表明：K17合金和NiCrAlY涂层在不同温度静态空气中氧化动力学曲线基本符合抛物线规律。900℃和1000℃时，K17合金上沉积NiCrAlY涂层后，明显改善了合金的抗氧化性。1100℃时，涂层的保护作用不如900℃和1000℃，900℃氧化时，NiCrAlY涂层氧化膜由α-Al2O3和Cr2O3的组成；1000℃氧化时，氧化初期，NiO,Cr2O3和Al2O3 3种氧化物同时生成。随着氧化的进行，不仅氧化膜增厚，而且发生较复杂的反应，氧化膜的相组成发生变化。随着氧化温度升高，涂层和基体之间元素扩散加剧，Ti从基体扩散到涂层表面形成氧化物是导致涂层抗氧化降低的原因。氧化膜从涂层上剥落下来，也导致了涂层抗氧化能力降低。     

真空热处理对镍基单晶高温合金溅射NiCrAlY涂层抗氧化性能的影响

用磁控溅射法在镍基单晶高温合金基体上沉积NiCrAlY涂层，研究了真空热处理对涂层组织结构及抗氧化性能的影响。结果表明，溅射NiCrAlY涂层主要由γ－Ni和β－NiAl两相组成，元素分布均匀；经真空热处理后，涂层主要由γ‘－Ni3Al、β－NiAl相和极少量的α－Al2O3相组成，元素分布变得不均匀，最外层富Al贫Cr。真空热处理可使溅射NiCrAlY涂层表面较早生成保护性能良好的α－Al2O3.1000℃氧化200h，溅射涂层氧化膜有较大部分已经剥落，但真空热处理涂层的氧化膜仍较好地粘附在涂层基体上。真空热处理使溅射NiCrAlY涂层表面生成的氧化膜粘附性更好，提高了溅射NiCrAlY涂层的抗氧化性能。     

γ-TiAl表面NiCrAlY/Al复合涂层的高温氧化行为

采用磁控溅射和电弧离子镀技术在γ-TiAl合金表面制备NiCrAlY/Al复合涂层,研究了复合涂层对提高γ-TiAl合金抗高温氧化性能的作用机理。经950℃恒温氧化100 h后,涂层表面未发现裂纹和脱落,涂层试样氧化增重值较基体大幅减小。对氧化层进行了SEM、EDS和XRD分析,结果表明无保护涂层的基体γ-TiAl合金表层疏松多孔,无法抵抗高温环境下氧气对基体合金的侵蚀。复合涂层表面的NiCrAlY镀层在氧化过程中形成了Cr2O3,α-Al2O3和β-NiAl相组成的致密防护涂层,阻隔了氧气与基体的接触,中间的Al层为表层持续生成Al2O3提供了Al源。NiCrAlY/Al复合涂层显著提高了基体在950℃下的抗高温氧化性能。     

渗铝改性离子镀NiCrAlY涂层的高温热腐蚀行为

为了进一步改善离子镀NiCrAlY涂层的抗热腐蚀性能,采用粉末包埋法在离子镀NiCrAlY涂层表面上进行渗铝,研究了涂层渗铝前后在850℃含氯硫酸盐膜下的热腐蚀行为.结果表明:在25%NaCl 75%Na2SO4熔盐中850℃热腐蚀40h时,未渗铝的NiCrAlY涂层生成的是外层以Cr2O3为主的氧化膜,渗铝后的NiCrAlY涂层仅生成一层Al2O3膜;未渗铝的NiCrAlY涂层在腐蚀50h后失去保护作用,而渗铝涂层在腐蚀100h后表面仍形成以Al2O3为主的保护膜.因此,渗铝处理可以明显提高原涂层的抗热腐蚀性能.     

搪瓷/NiCrAlY复合涂层的抗高温氧化及热腐蚀行为

研究了溅射NiCrAlY及搪瓷/NiCrAlY复合涂层在900℃空气氧化及850℃75mass%Na2SO4＋25mass%K2SO4和75mass%Na2SO4＋25mass%NaCl的热腐蚀行为.结果表明：溅射NiCrAlY涂层900℃表面生成了单一的氧化铝膜,具有良好的抗氧化性能,而搪瓷复合涂层进一步提高了NiCrAlY层的抗氧化性能;850℃两种盐的热腐蚀表明,基体合金没有出现内氧化及内硫化现象,搪瓷层的成分也没有显著变化,表现出优异的抗热腐蚀性能.     

梯度NiCrAlY涂层的1000和1100℃氧化行为研究

采用电弧离子镀技术及后续热处理工艺在镍基高温合金上制备了均匀NiCrAlY涂层和梯度NiCrAlY涂层,分析了2种涂层的组织结构,对比研究了2种涂层静态空气下1000和1100℃恒温氧化行为以及1100℃的循环氧化行为.结果表明:均匀NiCrAlY涂层由γ′/γ相和少量β-NiAl相、α-Cr相组成,成分分布均匀;梯度NiCrAlY涂层具有外层富Al和内层富Cr的结构,其中外层由β-NiAl相和少量γ′/γ相、α-Cr相组成.一方面,梯度涂层的初始Al含量较高;另一方面,氧化过程中其富Cr区两侧出现了对富Al区的Al向基体扩散起阻碍作用的Cr(W)析出带.这两方面使梯度涂层长时间维持更多的Al存储相,提升了氧化膜的迅速生成及再生成能力,从而使涂层具有较好的抗氧化性能.     

两种IC-6高温合金防护涂层的氧化行为

研究了IC-6高温合金及其防护性涂层NiCrAlY和NiCoCrAlY涂层在900～1100℃时的氧化.结果表明沉积NiCrAlY和NiCoCrAlY涂层后大大改善了IC-6合金的抗氧化性.在1000和1100℃时,NiCrAlY涂层的抗氧化性优于NiCoCrAlY涂层.900℃时,NiCrAlY涂层氧化膜主要是α-Al2O3,同时还含有少量的Cr2O3;而NiCOCrAlY涂层氧化膜为单一的α-Al2O3,但由于NiCoCrAlY涂层表面氧化膜不致密,降低了涂层的抗氧化性.1000℃氧化时,NiCrAlY涂层和NiCoCrAlY涂层的氧化膜主要由α-Al2O3和Cr2O3构成.     

退火处理对离子镀NiCrAlY涂层热腐蚀性能的影响

为了进一步改善离子镀NiCrAlY涂层的抗热腐蚀性能,对NiCrAlY涂层在1050℃进行真空退火2h,研究了涂层退火前后的热腐蚀行为.结果表明,退火处理消除了离子镀NiCrAlY涂层的一些孑L洞,涂层形成了γ/γ' β多相平衡组织,使涂层组织更致密;在25%NaCl 75%Na2SO4(质量分数)盐膜下850℃热腐蚀20h时,未退火的NiCrAlY涂层生成的是外层Cr2O3、内层Al2O3的双层氧化膜,退火后的NiCrAlY涂层仅生成一层Al2O3膜,孕育期增长,在一定程度上提高了抗热腐蚀寿命.     

空心阴极电弧镀NiCrAlY涂层的抗氧化性能

采用空心阴极电弧离子镀技术制备NiCrAlY涂层,研究涂层的高温抗氧化性能。结果表明涂层组织致密,与合金结合状态良好。电弧离子镀NiCrAlY涂层在1 100℃恒温氧化100h后增重只有2.22mg/cm2,在100次循环氧化后仍没有失重现象,其抗恒温氧化和抗循环氧化性能远优于成分相近的超音速火焰喷涂、爆炸喷涂和大气等离子喷涂的NiCrAlY涂层。电弧离子镀NiCrAlY涂层在恒温氧化和循环氧化过程中表面均形成了连续致密、粘附性的氧化铝保护膜。氧化膜没有翘起和剥落现象,涂层组织在氧化后仍然完整致密。热喷涂NiCrAlY涂层在上述氧化过程中则生成了保护性较差的Ni、Cr和Al混合氧化物,并发生了氧化膜剥落,同时有严重的内氧化现象。     

水蒸气对NiCrAlY涂层抗高温氧化性能的影响

采用热重分析及现代表面分析方法研究了低压等离子喷涂Ni CrAlY涂层在纯氧以及含5%水蒸气的O2中的高温氧化行为,结果表明：在纯氧的氧化环境中 ,NiCrAlY涂层氧化动力学遵循抛物线规律,在含有5％的水蒸气的O2中,NiCrAlY涂层在氧 化至110 h后氧化动力学几乎呈直线规律.XRD及SEM分析显示,NiCrAlY涂层在O2中氧化180 h后,表面形成一层致密的Al2O3;而在含5%水蒸气的O2中氧化180 h后表面氧化层中 除了有Al2O3外,还有NiO和Cr2O3.其原因在于水蒸气中的氢在氧化物中的溶解,致 使Ni2+扩散 速度增加,使氧化层变得疏松,降低其抗氧化性.     

THE CHARACTERISTICS OF OXIDE SCALE FORMED ON LOW PRESSURE PLASMA SPRAYED NiCrAIY COATING IN THE PRESENCE OF 5% WATER VAPOR

The oxidations of low pressure plasma sprayed (LPPS) NiCrAlY coating on nickelbase superalloy were studied at 1050C in flows of O2, and mixture of O2 and 5%H2 Ounder atmospheric pressure. Oxide formed on the surface of LPPS NiCrAlY coatingafter oxidation at 1050℃ in pure O2 consisted of NiCr2 O4, whereas oxide formed onthe surface of LPPS NiCrAlY coating after oxidation at 1000℃ in a mixture of O2 and5%H2 O is mainly composed of NiO. The effect of water vapor on the characteristicsof the oxide scale is attributed to the increase in Ni cation transport.     

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.     

Cyclic oxidation behavior of some plasma-sprayed coatings in Na2SO4-60%V2O5 environment

Cyclic oxidation behavior of plasma-sprayed NiCrAlY, Ni-20Cr, Ni₃Al, and Stellite-6 coatings was investigated in an aggressive environment of Na₂SO₄-60%V₂O₅ by thermogravimetric techniques for 50 cycles. These coatings were deposited on a Ni-base superalloy, namely Superni 600; 10Fe-15.5Cr-0.5Mn-0.2C-Bal Ni (wt.%). X-ray diffraction, scanning electron microscopy/energy dispersive x-ray (SEM/EDX), and electron probe microanalyzer (EPMA) techniques were used to analyze the oxidation products. The uncoated superalloy suffered accelerated oxidation in the form of intense spallation of its oxide scale. After deposition of the NiCrAlY coating, the superalloy showed a minimum mass gain, whereas after application of the Stellite-6 coating, a maximum mass gain was observed among the coatings studied. All of the coatings were found to be useful in reducing the spallation of the substrate superalloy. Moreover, the coatings were successful in maintaining continuous surface contact with the base superalloy during the cyclic oxidation. The phases revealed for the oxidized coatings were mainly the oxides of chromium and/or aluminum and the spinels containing nickel-chromium/cobalt-chromium/nickel-aluminum mixed oxides, which are reported to be protective against high-temperature oxidation/hot corrosion.     

Synthesis and oxidation behavior of nanocrystalline MCrAlY bond coatings

Thermal barrier coating systems protect turbine blades against high-temperature corrosion and oxidation. They consist of a metal bond coat (MCrAlY, M = Ni, Co) and a ceramic top layer (ZrO₂/Y₂O₃). In this work, the oxidation behavior of conventional and nanostructured high-velocity oxyfuel (HVOF) NiCrAlY coatings has been compared. Commercially available NiCrAlY powder was mechanically cryomilled and HVOF sprayed on a nickel alloy foil to form a nanocrystalline coating. Freestanding bodies of conventional and nanostructured HVOF NiCrAlY coatings were oxidized at 1000 °C for different time periods to form the thermally grown oxide layer. The experiments show an improvement in oxidation resistance in the nanostructured coating when compared with that of the conventional one. The observed behavior is a result of the formation of a continuous Al₂O₃ layer on the surface of the nanostructured HVOF NiCrAlY coating. This layer protects the coating from further oxidation and avoids the formation of mixed oxide protrusions present in the conventional coating. The original version of this article was published as part of the ASM Proceedings, Thermal Spray 2003: Advancing the Science and Applying the Technology, International Thermal Spray Conference (Orlando, FL), May 5–8 2003, Basil R. Marple and Christian Moreau, Ed., ASM International, 2003.     

Oxidation and hot corrosion of coated and bare oxide dispersion strengthened superalloy MA-755E

Cyclic hot corrosion and oxidation testing of an experimental oxide dispersion strengthened (ODS) superalloy MA-755E were conducted in a hot gas stream at Mach 0.3. The response of the ODS alloy, bare or with protective coatings, was similar to that of a conventional cast alloy, IN-792, in hot corrosion at 900°C. However, during oxidation at 1100 and 1150°C the ODS alloy differed from the cast alloy by developing a greater amount of subsurface porosity. Compared with a diffused aluminide coating, an electron beam vapor deposited NiCrAlY coating offered superior oxidation protection and decreased porosity formation. In additional testing, the tendency to form porosity was associated with the large grains of recrystallized powder metallurgy alloys but was independent of the presence of an oxide dispersion.     

NiCrAlY/Al-Al2O3/Ti2AlNb高温抗氧化和力学性能研究

采用电弧离子镀技水在NiCrAlY涂层与O相Ti₂AlNb合金之间沉积不同Al:Al₂O₃比例的Al-Al₂O₃薄膜作为扩散阻挡层.研究了900℃下恒温氧化500 h后NiCrAlY/Al-Al₂O₃/Ti₂AlNb体系中Al-Al₂O₃层阻挡合金元素互扩散的行为,以及对涂层氧化动力学曲线的影响.结果表明,没有添加扩散阻挡层的NiCrAlY/Ti₂AlNb体系,涂层和基体之间的元素互扩散十分严重,涂层丧失抗氧化能力;而添加扩散阻挡层的材料体系,涂层和基体之间的元素互扩散受到抑制,涂层的长期抗高温氧化性能得到提高.对于3Al-Al₂O₃,1Al-Al₂O₃和0Al-Al₂O₃ 3种扩散阻挡层,综合比较材料体系的抗氧化性能、阻挡层阻挡涂层和基体元素互扩散能力、以及涂层和基体之间结合力,当1Al-Al₂O₃薄膜作为扩散阻挡层时,材料性能最优异.同时,本文利用扩散阻挡系数简洁定量地表示出不同Al:Al₂O₃比例阻挡层的阻挡扩散能力.     

Hot-corrosion behavior of graded thermal barrier coatings formed by plasma-spraying process

The hot-corrosion behavior of thermal barrier coatings (TBCs) has been studied by comparing double-layer coatings and graded coatings. Two types of oxide ceramics, 2CaO·SiO₂-15mass%CaO·ZrO₂ (C₂S-15CZ) and 8 mass% Y₂O₃·ZrO₂ (8YSZ), with a bond coating of NiCrAlY, were applied to metallic substrates in this study. After hot-corrosion testing with V₂O₅-Na₂SO₄ corrosive ash for 3 h at 1273 K, the TBCs were investigated by visual inspection, a scanning electron microscope, x-ray diffraction, and electron probe microanalysis. The findings for the resulting coating of C₂S-15CZ reacted with V₂O₅ only where it was in direct contact with the corrosive ash. The affected area from the reaction was limited to the coating surface where V₂O₅ was present. The coating showed adequate hot-corrosion resistance against V₂O₅-Na₂SO₄ corrosive ash for 3 h at 1273 K. The findings for the 8YSZ coating were that Y₂O₃, the stabilizing component, particularly reacted with V₂O₅ and lost its function, which led to partial spalling of the coating. It was observed that the hot-corrosion resistance of the double-layer TBC was largely influenced by the performance of a corrosion-resistant NiCrAlY bond coat, which provided protection against corrosive components penetrating through the ceramic topcoat. Last, the graded coating degraded due to the oxidation of NiCrAlY particles that existed near the topcoat surface and affected the durability of the TBC.