溅射NiCrAlY涂层氧化过程Al2O3膜结构与形貌的转变

对溅射NiCrAlY涂层进行了900℃，1000℃，1100℃空 气中高温氧化。实验表明，氧化初期生成快速长大的亚稳态θ-Al2O3相，随着氧化时间 延长，θ-Al2O3逐渐转变成α-Al2O3，氧化动力学抛物线常数kp也随之下降 。θ→α-Al2O3相变速度与温度有关，温度越高，相变越快。对涂层进行真空热处理可 促进θ→α-Al2O3转变，使涂层表面快速形成保护性能优异的α-Al2O3。     

铂改性铝化物涂层的热生长层内应力研究

研究了镍基高温合金热障涂层系统中铂改性铝化物粘结层在空气中非连续高温氧化生成的Al2O3层内应力状态及相应的粘结层微观结构。利用Raman光激发荧光谱技术,发现铂铝粘结层在900℃氧化初期生成了θ-和α-Al2O3,而在1100℃氧化时,表面则形成连续致密的α-Al2O3层。通过α-Al2O3的光激发荧光谱偏移量,计算得到了热障涂层中热生长层的内压应力略高于3.0GPa。铂改性铝化物涂层表面Al2O3"背脊"处的内应力相对较低,同时由于没有陶瓷层的压制,生成的Al2O3起伏较大,并发生局部的Al2O3脱落。随氧化时间延长,由于Al元素沿晶界扩散较快,导致更多的γ′-Ni3Al在粘结层晶界处形成,粘结层中基本相β-NiAl向γ′-Ni3Al转变,改变了粘结层本身的热膨胀系数,引起热生长层中内应力变化。     

电弧离子镀NiAlHf涂层的抗高温氧化性能

目的通过电弧离子镀技术,获得抗氧化性能优良的NiAl涂层。方法采用电弧离子镀技术,在弧流为110 A,偏压为-50 V的参数下沉积NiAlHf涂层。通过X射线衍射仪(XRD)和扫描电子显微镜(SEM)对涂层的物相结构和形貌进行分析,通过能谱仪(EDS)分析涂层的成分。采用恒温氧化增重实验对涂层的氧化动力学进行分析。结果由电弧离子镀技术制备的NiAl涂层致密均匀,无大颗粒、孔洞等缺陷。涂层主要由β-NiAl相组成,活性元素Hf固溶在主相中。NiAlHf涂层表现出良好的抗高温氧化性能,动力学曲线符合抛物线规律,在1150℃下恒温氧化200h的平均氧化速率为0.0841g/(m^2×h),远优于传统MCrAlY涂层体系。NiAlHf涂层在氧化初期形成保护性的α-Al2O3氧化皮以及少量亚稳态的θ-Al2O3,随后θ-Al2O3逐渐转变为稳态的α-Al2O3。Hf在涂层表面富集从而形成HfO2,对氧化皮形成了钉扎作用,增强了氧化皮的粘附性,提高了涂层的抗氧化性能。随着氧化的进行,涂层中的β-NiAl相逐渐转变为γ'-Ni3Al相。结论 NiAlHf涂层在1150℃下仍具备优良的抗高温氧化性能,对下一代耐更高温度涂层开发,电弧离子镀NiAl涂层的技术推广及工业化应用有一定的指导作用。     

Comparison of molybdenizing and NiCrA1Y coating on Ti and Ti-6A1-4V

Two surface treatments, molybdenizing and depositing NiCrAIY coating, were applied to improve the microhardness and the oxidation re-sistance of titanium and Ti-6Al-4V. Coupons were analyzed using optical microscopy (OM), scanning electron microscopy (SEM) with X-ray energy dispersive spectrometer (EDS), and X-ray diffraction (XRD). Vickers hardness and isothermal oxidation tests were carded out to evaluate the effects of these two surface treatments on the microhardness and oxidation resistance of the substrates. The post vacuum heat treatment of the NiCrAlY coating and the molybdenizing parameters were also discussed. It is found that molybdenizing can obviously in-crease the surface hardness of titanium due to the formation of β,α", and α' phases in the diffusion layer. As γ' phase is formed after vacuum heat treatment, the NiCrAIY coating is effective in improving the surface hardness of Ti-6Al-4V. The NiCrAlY coating can obviously de-crease the oxidation rate of Ti-6Al-4V at 700-900℃, which can be attributed to the formation of Al2O3 and Cr2O3 mixed scale during the oxidation.     

Re对NiCrAlY涂层热腐蚀行为的影响

通过电弧离子镀制备了NiCrAlYRe和NiCrAlY涂层,经真空热处理后涂层均由γ´-Ni₃Al、γ-Ni、 β-NiAl和α-Cr四相构成。在NiCrAlYRe涂层中,Re主要存在于α-Cr相,Re促进了α-Cr相在涂层中的析出,并提高了α-Cr在长期氧化过程中的稳定性,特别在氧化膜/涂层界面上析出了大量富Re的α-Cr。由于富Re的α-Cr 同α-Al₂O₃具有极为接近的热膨胀系数,降低了氧化膜中的热应力,提高了NiCrAlY 涂层表面抗剥落能力。添加Re明显提高了NiCrAlY涂层在900℃90%Na₂SO₄+ 10%K₂SO₄介质中的抗热腐蚀性能。     

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.     

EFFECT OF MICROSTRUCTURE CHANGE ON OXIDE FORMATION OF SPUTTERED Ni-3Cr-10Al NANOCRYSTALLINE COATING

1.IntroductionThesputterednanocrystallinecoatingswiththesameconlpositionasthesubstrateweresuccessfullyappliedtoK38G[ll,Kl7F[2]lLDZc5[3]Ni-basetlsuperalloys.Themaincharacterizati0nisthatnan0crystallizati0ncouldimpr0vetheselectiveoxidationofAl,therefore,thetransiti0nfr0minternalt0externaloxidati0nofAlisrealizedandanex-ternalAl2O3scaleisfOrn1ed.Niisthemainingredient0fNi-basedsuperal1oysandtheeffectivenessofthesesuperal1oysdependsgreatly0ntllepresellceofAlorCrtoformaprotectivelayerofAl2O:jo…     

Cyclic oxidation of Pt/Pd-modified aluminide coating on a nickel-based superalloy at 1150 °C

Pt-, Pd-, and Pt/Pd-modified aluminide coatings were prepared on Inconel 738LC by pack aluminizing at 1034 °C. During pack aluminizing, Pt-modified aluminide coating formed a two-phase β-NiAl + PtAl₂ layer and a β-NiAl layer on an interdiffusion zone, whereas Pd- and Pt/Pd-modified aluminide coatings formed only the thicker β-NiAl layer. However, Pd-modified aluminide coating had many pores. During cyclic oxidation, Pt/Pd-modified aluminide coating had a surface that was less rumpled than that of Pt-modified aluminide coating due to its thicker thickness. Pt/Pd-modified aluminide coating had a 22% greater Al-uptake than Pt-modified aluminide coating. Cyclic oxidation tests at 1150 °C showed that Pt/Pd-modified aluminide coating had the best cyclic oxidation resistance. After the cyclic oxidation, an additional γ-Ni phase was seen beneath the outermost alumina scale on the the γ′-Ni₃Al phase in Pt/Pd-modified aluminide coating. The γ-Ni phase, which had a higher Cr content, increased the adhesion and stability of the alumina.     

Pd-Ni-Al涂层的高温短期氧化行为

在M38镍基高温合金上电镀Pd-20 mass%Ni合金，采用低压固体粉末包埋渗铝方法制备钯改性铝化物涂层，XRD分析表明，涂层主要由β-(Ni,Pd)Al相组成.利用TGA、SEM等方法，研究了涂层在800℃、900℃和1100℃的高温氧化行为表明，β-(Ni,Pd)Al涂层恒温氧化动力学遵循抛物线规律；1000℃氧化动力学则不遵循抛物线规律.在800℃和900℃下，β-(Ni,Pd)Al 涂层表面氧化产物包括α-Al2O3、θ-Al2O3和少量的γ-Al2O3；在1000℃下，涂层表面存在α-Al2O3和θ-Al2O3两种氧化物；在1100℃下，涂层表面氧化产物主要是α-Al2O3.此外，在各温度下涂层表面的氧化产物中都含有少量的TiO2，随着温度升高，其含量增加.     

溅射NiCrAlY渗Al涂层的高温氧化行为

用SEM、XRD和EPMA等手段,研究了溅射NiCrAlY涂层渗Al前后在1000℃和1100℃的高温氧化行为.结果表明,溅射涂层在1000℃形成了单相的α-Al2O3,具有优异的抗氧化性能;但在1100℃由于Al的过度消耗而失去保护作用.渗Al涂层在1000℃快速增长θ-Al2O3相,使其抗氧化性能稍逊于溅射涂层;在1100℃表面形成了以α-Al2O3为主的保护膜,抗氧化性能优于溅射涂层.     

共渗制备NiCrAlY涂层及抗高温腐蚀研究

采用热扩散的方法在高温合金K417G基体上制备了NiCrAlY涂层,经测定,涂层以β–NiAl相为主,Cr以固溶态和AlCr(x)相同时存在。1000和1100℃恒温氧化试验表明,NiCrAlY涂层显著提高了合金的抗氧化性,氧化膜致密稳定的Al2O3为主,300h后氧化膜没有明显的剥落。对基体合金和涂层试样进行了900℃,NaCl/Na2SO4(25:75)融盐环境的热腐蚀试验。结果表明,NiCrAlY涂层氧化膜完整,涂层内硫化物含量低,有效提高了抗热腐蚀性能。     

EFFECT OF NANOCRYSTALLIZATION ON THE SCALING OF NiAl AT 1000℃ IN AIR

The oxidation behavior of a magnetron sputtered nanocrystalline NiAl coating was investigated at 1000℃ in air. Comparing with cast NiAl and NiAl-0.1at.%Y alloys reveals influences of nanocrystallization as well as yttrium addition on the oxidation behavior of NiAl. Results show that a phase transformation from metastable θ-Al2O3 to stable a-Al2O3 occurred in scales, which was accelerated by the microcrystallization and retarded by the addition of Y. The addition of Y as well as the nanocrystallization reduced the void formation at the interface between the scale and the substrate.     

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.     

Comparison of molybdenizing and NiCrAlY coating on Ti and Ti-6Al-4V

Two surface treatments, molybdenizing and depositing NiCrAlY coating, were applied to improve the microhardness and the oxidation resistance of titanium and Ti-6Al-4V. Coupons were analyzed using optical microscopy (OM), scanning electron microscopy (SEM) with X-ray energy dispersive spectrometer (EDS), and X-ray diffraction (XRD). Vickers hardness and isothermal oxidation tests were carried out to evaluate the effects of these two surface treatments on the microhardness and oxidation resistance of the substrates. The post vacuum heat treatment of the NiCrAlY coating and the molybdenizing parameters were also discussed. It is found that molybdenizing can obviously increase the surface hardness of titanium due to the formation of β, α″, and α′ phases in the diffusion layer. As γ′ phase is formed after vacuum heat treatment, the NiCrAlY coating is effective in improving the surface hardness of Ti-6Al-4V. The NiCrAlY coating can obviously decrease the oxidation rate of Ti-6Al-4V at 700–900°C, which can be attributed to the formation of Al₂O₃ and Cr₂O₃ mixed scale during the oxidation.     

Microstructural Characteristics and Oxidation Behavior of Low-Pressure Cold-Sprayed CoNiCrAlY Coatings

CoNiCrAlY coatings were deposited by low-pressure cold spraying and subsequently heat-treated at 1050 °C for 4 h in a vacuum environment. The microstructural characteristics and oxidation behavior of CoNiCrAlY coatings were investigated. The as-sprayed coating exhibited low porosity and oxygen content. The high plastic deformation of the sprayed particles led to significant refinement of γ-matrix and dissolution of β-(Ni,Co)Al phase in the as-sprayed coating. After heat treatment, the single phase (γ) in the as-sprayed coating was converted into a γ/β microstructure, and a continuous single α-Al₂O₃ scale was formed on the coating surface. Vacuum heat treatment can postpone the formation of spinel oxides within 100 h. After being oxidized at 1050 °C for 400 h, the heat-treated coating exhibited better oxidation resistance than the as-sprayed coating. The reduced growth rate of the oxide scale and the suppression of the formation of spinel oxides can be attributed to the vacuum heat treatment, as well as the intrinsic microstructure of the cold-sprayed coating. Finally, the effects of the microstructural changes induced during the cold spraying process on the growth of the thermally grown oxide and the oxidation mechanisms of the CoNiCrAlY coatings were discussed.     

Microstructures of thin and thick slurry aluminide coatings on Inconel 690

Two slurry aluminide coatings are produced on the Ni-base super alloy Inconel 690 by applying two different thicknesses of the same slurry on to the 690 substrate, followed by a two-step heat-treatment. The resulting thin aluminide coating consists of a single layer of Ni-rich β-NiAl matrix containing few large Cr precipitates with a high P content. The thick aluminide coating has a precipitate free inner layer of Ni-rich β-NiAl. An outer layer of Al-rich β-NiAl with many α-Cr precipitates has formed as well. The present metallurgical characterization shows a significant influence of slurry thickness on the morphology and composition of the coatings formed during heat treatment.     

阴极微弧电沉积表面处理钛的高温氧化行为

在0.4 mol/l Al(NO3)3乙醇溶液中,采用阴极微弧电沉积方法在纯钛表面制备出80 μm厚的氧化铝涂层.研究了钛及其镀膜样品在973 K的高温氧化行为,并分析了它们恒温氧化后的组织、成分和相组成.结果表明,具有氧化铝涂层的钛在973K的氧化速率降低了4倍,恒温氧化后涂层的形貌和相组成几乎保持不变.涂层/钛界面附近的较薄氧化铝致密层对抑制氧和钛原子的扩散起重要作用.阴极微弧电沉积是提高钛抗氧化性能的有效方法之一.     

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.     

微晶化对Ni-5Cr-5Al合金氧化产物的影响

利用磁控溅射在Ｎｉ－５Ｃｒ－５Ａｌ（原子数,％）合金上制备与基体相同成分的微晶涂层,获得的涂层在１０００℃空气进行了氧化实验。结果表明,２００ｈ氧化后涂一成了分层结构的氧化膜：外层为ＮｉＯ和ＮｉＡ１２Ｏ４,内层为连续致密的α－Ａ１２Ｏ３。微晶化使得Ｎｉ－Ｃｒ－Ａｌ系三元合金表面生成一层连续Ａ１２Ｏ３所需的Ｃｒ、ＡＬ含量大大降低。     

高强度铝合金微等离子体电解氧化陶瓷质膜层影响因素

微等离子体电解氧化是在阳极氧化基础上发展起来的直接在轻合金表面原位生成γ-Al2 O3和α-Al2 O3陶瓷质膜的一项表面工程新技术.α-Al2 O3对陶瓷质膜层的性能起决定性作用,最大限度地促进α-Al2 O3的形成,是改善铝合金表面综合性能的关键.经过对国内近20个单位的调研,发现该技术在军工、航空、航天、机械等领域有着迫切的需求和广泛的应用前景,有望部分替代硬质氧化膜实现大规模生产.本文从基体材料、溶液特性及电参数三方面分析铝合金微等离子体氧化膜层的影响因素,重点分析基体合金元素对陶瓷质膜层的影响.指出该技术在高强度铝合金应用领域的发展方向并对其前景进行了展望.