金属-氧化物扩散障对涂层和基体间元素互扩散的阻碍作用

本文研究了低压等离子喷涂的Ni_3Al-Y_2O_3扩散障层对外层涂层与基体间元素互扩散的阻碍作用,发现阻碍扩散的作用与扩散障层中氧化物含量有关。当Y_2O_3含量为8wt-%时,扩散障对元素互扩散没有明显的阻碍作用;当Y_2O_3含量为30wt%时,对Al,Co和Cr等元素的扩散有明显的阻碍作用。并且,阻碍作用随元素不同而不同。     

Oxidation protection of NiCoCrAlY coatings on γ-TiAl

The effect of NiCoCrAlY overlay coatings on the oxidation resistance of γ-TiAl was studied at 900 ℃ in static air. To hinder the interdiffusion of the elements, the Al/Al2O3 layer was added between the coating and the alloy. The results show that the TiAl alloy exhibits poor oxidation resistance. NiCoCrAlY coating can not effectively protect the γ-TiAl substrate from high temperature oxidation because of the serious interdiffusion between the coating and the substrates. With Al/Al2O3 diffusion barrier, the NiCoCrAlY coating exhibits excellent oxidation protection on γ-TiAl alloy.     

Statistics of oxidation resistance of Ni-(0-15)Co-(8-15)Cr-(0-5)Mo-(0-10)W-(3-8)Al-(0-5)Ti-(0-10)Ta-0.1C-0.01B superalloys at 1000℃ by compositional variations

The effects of alloying elements(Co,Cr,Mo,W,Al,Ti,and Ta) on the oxidation resistance of Ni-(0-15)Co-(8-15)Cr-(0-5)Mo-(0-10)W-(3-8)Al-(0-5)Ti-(0-10)Ta-0.1 C-0.01 B alloys were studied.The sample compositions were designed by the Box-Behnken method of design of experiments(DOE).The alloying elements show complicated effects on the mass gain due to oxidation,depending on the alloy composition.Al reduces the mass gain largely.The other elements except Al do not appear to exert a strong effect on the oxidation rate on average,but their influences are shown clearly in the alloys with a low Al content.Co,W,and Ta reduce the oxidation rate,while Cr,Mo,and Ti promote oxidation.Ta is the most effective element in reducing the oxidation rate of the alloy with a low Al concentration.It is confirmed that a continuous Al_2O_3 layer is essentially required for high oxidation resistance.The oxide scale of easily oxidized alloys has various oxides such as NiCr_2O_4,NiAl_2O_4,NiO,Cr_2O_3,CrTaO_4,and TiO_2.     

Interdiffusion in the Face-Centered Cubic Phase of the Co-Al-W-Ta System Between 1090 and 1240 °C

Interdiffusion of Al, W, Ta and Co in a Co-base alloy at temperatures between 1090 and 1240 °C has been investigated. The interdiffusion coefficients were found to be close to those reported for these elements in Ni-base alloys. Combining the diffusion simulation software DICTRA with the Ni-base diffusion databases TCNi₅ and MobNi₃, the interdiffusion profiles of Co, Al W, and Ta were modeled for Co9Al8W2Ta/Co diffusion couples annealed at different temperatures and for different times. The results show that interdiffusion in the Co-Al-W-Ta alloys can be modeled reasonably well using the available commercial databases for thermodynamics and kinetics of Ni-base systems.     

Oxidation Performance and Interdiffusion Behaviour of two MCrAlY Coatings on a Fourth-Generation Single-Crystal Superalloy

The oxidation behaviour of a fourth-generation single-crystal superalloy without coating and with two types of MCrAlY coatings at 1140 °C was studied. The results showed that both coatings greatly improved the oxidation resistance of the superalloy, and the addition of Hf further improved the oxidation resistance by pinning the oxide layer into the coating. Before and after oxidation, obvious Cr and Al interdiffusion was detected. Inward Cr diffusion induces the precipitation of a topologically close-packed phase, while the diffusion of Al affects the structure of the γ/γ' phase, the solubility of refractory elements, and the formation of an interdiffusion zone.     

微量元素对低膨胀Fe-Ni基高温合金抗氧化性能的影响

为了保持低的膨胀系数,低膨胀GH909合金中不含Cr,导致合金的抗氧化性能较差为了解决这一问题,在GH909合金的基础上调整成分,加入少量Cr和稀土元素Y与La等,并提高Co/(Co+Ni)比例,使合金在膨胀系数基本未变的情况下,抗氧化性能得到较明显的改善用X射线衍射、金相显微镜、扫描电镜等检查了合金的氧化层,发现GH909合金氧化层很厚,其主要成分为Fe3O4,Fe3O2等,氧化层组织较疏松,有内氧化现象.加入Cr和稀土元素的合金氧化层较薄,氧化层主要成分还有Cr2O3等,氧化层组织致密,未见内氧化.温度愈高,Cr和稀土的有益效果愈明显,它们有效地抑制了氧的扩散.     

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.     

DETERMINATION OF ACTIVITY OF AI IN SOLID Cu-Al ALLOYS

Activities and activity coefficients of Al in solid Cu-AI alloys have been determined by meansof solid electorlyte galvanic cells Al(a_1 , in alloy), Al_2O_3 | ZrO_2· Y_2O_3 | Ni, NiOand Al(a_1 , in alloy), Al_2O_3 | Na, βAl_2O_3 | Al(a_2 , in alloy), Al_2O_3     

The Improvement of Oxidation Resistance of a Re-Based Diffusion Barrier/Ni�CAl Coating on the Single-Crystal Ni-Based TMS-82+ Superalloy

Oxidation behavior of a Re-based diffusion barrier/Ni?CAl coated single-crystal (SC) Ni-based TMS-82+ superalloy was studied to compare with those of the base and Ni?CAl coated superalloys under cyclic air at 1150 °C for 200 h. The base superalloy showed a negative mass gain due to extensive oxide spallation, and the Ni?CAl coated superalloy without the diffusion barrier started to spall slightly after about 90 h. The oxidation resistance of the Ni?CAl coated superalloy with the Re-based diffusion barrier was greatly improved due to the formation of a dense ??-Al₂O₃ layer in the scale. The Re-based alloy was an effective diffusion barrier layer against inward diffusion of Al and outward diffusion of alloying elements in the alloy substrate due to the reduced thickness of interdiffusion zone with small amount of detrimental precipitates and higher content of Al in the Ni?CAl coating that supplied enough Al for formation of the ??-Al₂O₃ layer.     

“A study on the effect of Co,Cr and Ti on the corrosion of FE40AL intermetallic in molten NaCl–KCl mixture”

The effect of the addition of 3 at% Cr, Co or Ti on the corrosion behavior of Fe40Al intermetallic alloy in 1 M NaCl:1 M KCl mixture at 750 °C has been carried out by using electrochemical techniques. Techniques included potentiodynamic polarization curves, linear polarization resistance and electrochemical impedance spectroscopy measurements. It has been found that the addition of either Cr, Co or Ti decreased the corrosion rate of Fe40Al intermetallic by almost five times due to the formation of a passive layer, absent in the base alloy. This was because the diffusion of Al towards the top of the alloy for the establishment of a protective Al₂O₃ layer was enhanced by the presence of these alloying elements. The corrosion rate for the base alloy was under diffusion control of the reactants, whereas that for alloyed intermetallic was under charge transfer control.     

锆合金包壳Cr涂层界面元素扩散行为研究进展

随着核反应堆向高燃耗和更长服役寿命方向发展,对包壳材料的安全可靠性提出了更高的要求。锆合金表面Cr涂层由于其优异的抗高温氧化性能、耐腐蚀性能以及与基体良好的兼容性,被认为是最有前景的耐事故涂层包壳材料。综述了近年来涂层Cr与基体Zr界面元素扩散行为的研究成果,重点介绍了Cr涂层不同状态下的界面结构及演变规律,包括沉积、退火、辐照、氧化等状态。总结了Cr的扩散、分布和金属间化合物Zr-Cr-(Fe)层的生长动力学模型,归纳了界面扩散对涂层结构及性能的不利影响。扩散阻挡层是一种抑制涂层与基体互扩散的有效结构,介绍了阻挡层设计制备原则以及现有的和潜在的金属或陶瓷阻挡层材料,分析了2类典型阻挡层的优缺点。金属阻挡层能抑制Cr的扩散并延迟Cr-Zr共晶反应,但需要考虑中子经济性;虽然陶瓷阻挡层阻隔元素扩散的性能优异,但由于其与锆合金力学性能和热膨胀系数的差异明显,易产生微裂纹,需要考虑其抗裂性。最后提出了采用实验与分子动力学等相结合的多尺度研究方法开展界面研究,同时指出了目前研究工作中亟待解决的关键问题,这为后续的锆合金表面耐事故涂层研究与开发提供了重要参考。     

Factors affecting the microstructure of platinum-modified aluminide coatings during a vapor phase aluminizing process

Platinum (Pt)-modified aluminide coatings were developed by electroplating a thin layer of Pt followed by an industrial vapor phase aluminizing process. The goal of this work was to systematically investigate the effect of critical coating process parameters (such as the electroplated Pt thicknesses, Al contents in Cr-Al nuggets, diffusion heat treatments) and substrates on the final Pt-modified aluminide coatings. Surface morphology and cross-section microstructure of the developed coatings were inspected and compared by using Optical Microscope, Scanning Electron Microscope (SEM) equipped with energy dispersive spectroscopy (EDS). Experimental results showed that the Al and/or Pt increase shall favor the formation of ξ-PtAl₂ phase; transformation of ξ-PtAl₂ into β-(Ni,Pt)Al phase can be obtained via a heat treatment process; Cr, Co elements in the studied Ni-base superalloy substrates did not show significant influence on coating outer layer microstructure; while substrate elements affect the microstructure of the coating interdiffusion layer.     

电泳共沉积NiCoCrAlY粘结层制备及抗高温氧化研究

目的 分析研究Ni基合金与粘结层之间的扩散和界面反应规律,以及其对热障涂层的抗高温氧化性能和工作寿命的影响.方法 采用电泳共沉积、真空致密化处理,在K17镍基高温合金表面制备NiCoCrAlY粘结涂层,并进行1000℃×100 h抗高温氧化实验,采用XRD、SEM、EDS分析NiCoCrAlY粘结涂层在高温氧化过程中合金元素的扩散规律.结果 高温氧化动力学曲线表明,氧化100 h制备的NiCoCrAlY粘结涂层的氧化速率为17.2134 mg/cm2,远低于K17镍基高温合金的.Ni由涂层向基体内扩散,Cr和Co向外扩散,Al向界面处扩散.电泳沉积制备的NiCoCrAlY粘结层经真空致密化处理后,涂层均匀、致密,粘结层主要由Ni3 Al、Al3 Y5 O12、Cr23 C6以及α-Al2 O3等组成.结论 NiCoCrAlY粘结涂层的抗高温氧化性高于K17镍基高温合金,在高温氧化过程中,α-Al2 O3氧化膜提高了NiCoCrAlY粘结涂层的高温抗氧化性.Ti主要来自基体的缺陷中,随着高温氧化作用,获得了由基体向外扩散所需要的能量,并且同时与氧反应生成TiO,TiO容易在粘结层表面形成泡状物质,Ti的扩散对粘结层的致密度与均匀度造成一定的影响.     

等离子体电解阴极沉积Y2O3陶瓷涂层

在Y（NO3）3水溶液中,以Fe25Cr5Al合金为阴极,研究了等离子体电解阴极沉积Y2O3陶瓷涂层的规律。研究发现,当施加的槽电压超过临界值时,阴极发生气膜微弧放电,在合金表面沉积出Y2O3陶瓷涂层。研究了施加槽电压、沉积时间、Y（NO3）3浓度对沉积Y2O3陶瓷涂层的影响。扫描电镜（SEM）、X射线衍射（XRD）分析结果表明,获得的Y2O3陶瓷涂层表面具有熔融的特征,涂层致密与基体结合牢固。探讨了等离子体电解阴极沉积Y2O3涂层的机理。     

Y_(0.08)Sr_(0.92)TiO_(3+δ)/Gd_(0.2)Ce_(0.8)O_(1.9)双相混合导体合成及在氧传感器中应用

以SrCO_3、TiO_2、Y_2O_3、CeO_2及Gd_2O_3为原料,用传统固相烧结法在不同温度下制备了一系列比例(体积比)的Y_0.08Sr_0.92TiO_(3+δ)/Gd_0.2Ce_0.8O_1.9(CGO)双相复合混合导体材料.用Archimedes法、SEM 、XRD、 EIS等手段对材料的致密度、微观结构、化学相容性及导电性能进行了研究.结果表明,1600 ℃烧结的40% (体积分数, 下同)YST/60% CGO的试样相对体密度达到了99%,未发生相转变,化学相容性较好且电导率较高.以40%YST/60%CGO的粉体作为混合导体制备极限电流传感器,进行O_2敏感性能测试.结果表明:传感器在氧浓度低于0.1%,温度范围在600～700℃内,极限电流随氧浓度增大而增大,二者具有较好的线性关系.实验证明YST/CGO混合导体材料可以作为限流型氧传感器的扩散阻使用.     

Influence of aluminium on the microstructure of Co based alloy coatings

Abstract

Coating contamination as a consequence of the diffusion of elements from the operating environment, accounts for the deterioration of a variety of mechanical components, and is particularly severe on those that operate at elevated temperatures. This study analysed the degradation of three Co based alloy coatings as a consequence of their contamination with Al. One Co–Cr–W and two Co–Cr–Mo–Si atomised alloy coatings, each with and without 5 wt-% aluminium powder, were deposited by plasma transferred arc on AISI 316L stainless steel plates. Accelerated aging at 600 and 1000°C contributed to the understanding of the effect of Al on the microstructure of coatings. Coatings with and without Al were characterised by laser confocal microscopy and microhardness. Dilution increased on coatings modified with Al due to the exothermic synthesis of aluminide compounds and the most significant microstructure modification was observed in the Co–Cr–Mo–Si coatings as primary Laves phase was almost suppressed. Accelerated aging tests showed that aluminium had a deleterious effect on the three Co based coatings although it was more pronounced in those processed with the Co–Cr–W alloy.     

Ti_3Al及其渗铝涂层的热腐蚀性能

采用电化学方法并结合各种物相分析技术研究了Ti_3Al金属间化合物在熔融(Na,K)_2SO_4-NaCl中的热腐蚀行为及渗铝涂层对其耐蚀性能的影响。结果表明,Ti_3Al耐热腐蚀性能较差。形成了外层为TiO_2,中间层为富铝的TiO_2-Al_2O_3复合层,内层为富铌的Nb_2O_5-TiO_2-Al_2O_3层的三层结构。渗铝涂层能在合金表面形成Al_2O_3氧化膜而明显改善Ti_3Al的耐蚀性能。     

Diffusion barrier behaviors of (Ru,Ni)Al/NiAl coatings on Ni-based superalloy substrate

For Ni-based single crystalline superalloy with high temperature protective coatings, the formation of detrimental phases in the superalloy substrate resulting from interdiffusion between the coatings and the substrate significantly degrades the mechanical properties of the substrate. In this paper, a novel (Ru,Ni)Al/NiAl diffusion barrier coating was produced by electrodeposition of Ru together with electron beam-physical vapor deposition of Ni–Al layer. The microstructure and diffusion barrier behavior of the (Ru,Ni)Al/NiAl coating was investigated by scanning electron micrograph (SEM) equipped with energy dispersive spectroscopy (EDS). SRZ mainly consisting of P phase and other TCP phases were presented beneath the NiAl coating due to the interdiffusion between the coating and Ni-based superalloy. The (Ru,Ni)Al layer effectively slowed down inward diffusion of Al from the coating and outward diffusion of alloying elements such as W and Mo, therefore suppressed the formation of TCP phases and SRZ.     

Y2O3改性渗铝工艺及渗层抗高温氧化性研究

采用在20钢上复合电镀Ni-Y2O3层后再扩散渗铝的方法，得到了Y2O3改性的渗Al复合层，并对渗层氧化性能进行了试验研究。SEM及EDXA观察结果表明，经Y2O3改性的渗层，Y2O3颗粒均匀分布于渗层中，且表面铝含量达到30．65％。不连续氧化和循环氧化试验的结果表明，其抗高温氧化性能明显提高，分别为纯铝渗层的2．5倍和3倍。     

钇对IN-939抗热腐蚀性的影响

本文研究了钇对铸造镍基高温合金IN—939热腐蚀性能的影响,采用75％Na_2SO_4—25％NaCl为付蚀介质的坩埚法,在温度为850℃与900℃,时间从10小时到300小时的范围内进行实验。 从热付蚀减重及渗透深度测得的动力学曲线表明:钇能改善合金热付蚀性。对热付蚀产物进行了金相显微镜和扫描电镜观察以及电子探针与X射线衍射分析。观察到含钇合金付蚀层的表面形貌与不含钇合金有明显区别,IN—939合金表面上形成的付蚀层为氧化铬和硫化铬等的多层结构,其下为铬的贫化区;而IN—939Y表面付蚀层是由大量的氧化铬少量的TiO_2,α—Al_2O_3及微量Y_2O_3、YCrO_3与硫化物组成。腐蚀层下没有贫铬现象,而出现贫钛区与沿晶界的内氧化物以及钇与钛的硫氧化物的分散质点。