稀土元素Ce与Y对JG4246A合金高温氧化行为的影响

在第二代高温合金JG4246A中分别添加不同含量的稀土元素Ce和Y,得到含0.012Ce(质量分数,%,下同)、0.017Ce、0.034Y、0.061Y四种合金铸锭,研究了在1100℃下Ce与Y对合金高温抗氧化性能的影响。采用X射线衍射仪(XRD)及扫描电镜(SEM)分析了氧化膜的物相组成以及氧化表面的形貌。结果表明,JG4246A合金在1100℃空气中恒温氧化过程中,添加稀土元素可以减少合金的氧化质量增加,氧化动力学符合抛物线规律;相对于稀土元素Y,Ce对减缓JG4246A合金的高温氧化速率的作用更显著;稀土元素的添加没有改变氧化膜的表面形貌,但是生成的尖晶石型氧化物使氧化膜更加致密,能够抑制阳离子的向外扩散,降低氧化反应速率,从而提高高温抗氧化性能。     

离子注入Ce+的Ni20Cr合金在1050℃空气中氧化动力学特征

采用热重分析方法研究了Ni20Cr及经预氧化处理后的合金表面离子注入Ce+后在1050℃空气中的恒温氧化动力学及循环氧化行为.结果表明,离子注入对经预氧化处理后合金氧化行为的影响与合金表面直接注入的效应类似,可降低合金氧化速率和改善氧化膜粘附性.认为抗氧化性能的提高与Ce+改变氧化机制及降低氧化膜/合金界面处因阳离子向外扩散产生的空位数量有关.     

SEM INVESTIGATION ON HIGH TEMPERATURE OXIDATION OF Fe-23Cr-6Al ALLOYS (WITHOR WITHOUT La, Ce AND Y ADDITIONS)

本文以扫描电镜(带X射线波长谱仪)为主要工具,对Fe-23Cr-6Al合金(不含稀土及加La,Ce和Y)1300℃高温氧化进行了研究.阐明了不含稀土合金氧化皮粘附性极差的根源,是部分向外扩散的阳离子留在氧化皮/基体界面处的空位聚集成空腔,使氧化皮和基体产生部分脱离的缘故.并认为添加稀土改变氧化皮的生长机制,是稀土改善Fe-Cr-Al合金高温氧化皮粘附性的主要原因.     

Fe-23Cr-6Al合金(不含稀土及加La,Ce和Y)高温氧化的扫描电镜研究

本文以扫描电镜(带X射线波长谱仪)为主要工具,对Fe-23Cr-6Al合金(不含稀土及加La,Ce和Y)1300℃高温氧化进行了研究.阐明了不含稀土合金氧化皮粘附性极差的根源,是部分向外扩散的阳离子留在氧化皮/基体界面处的空位聚集成空腔,使氧化皮和基体产生部分脱离的缘故.并认为添加稀土改变氧化皮的生长机制,是稀土改善Fe-Cr-Al合金高温氧化皮粘附性的主要原因.     

Ce对Ni—Cr—Cu合金抗氧化性的影响

作者研究了添加0.1％和0.8％Ce的Ni—Cr—Cu合金在空气中1200℃100小时等温氧化和500小时循环氧化。Ni—Cr—Cu合金中添加微量Ce后,显著降低了氧化速率,增加了氧化膜的剥落抗力。氧化速率降低是添加Ce后各种效应综合作用的结果。它们是:(1)由于Cr的扩散加快,富Cr保护膜更迅速形成;(2)聚集在膜/合金界面附近的含Ce氧化物与空位复合,减少了膜/合金界面的空洞;(3)固溶于氧化膜中的含Ce氧化物阻碍了Cr~(3+)沿氧化物晶界的短程扩散。 提高耐剥落抗力主要原因是:(1)添加Ce使氧化膜晶粒变细,从而改善了塑性变形和适应热应力的能力;(2)0.8Ce合金中稀土氧化物“钉扎”(Keying)作用改善了膜与合金粘附性,并改变了热应力的分布状态。     

形状记忆合金Ti44Ni47Nb9的抗高温氧化性能

采用恒温氧化法，结合X射线衍射(XRD)、扫描电镜(SEM)及能谱分析(EDS)等手段，研究了Ti44Ni47Nb9形状记忆合金(SMA)的抗高温氧化性能．结果表明，Ti44Ni47Nb9合金在450℃下轻微氧化；600—800℃高温下氧化增重曲线符合抛物线规律，氧化膜外层主要是金红石型TiO2，中间为富Nb层，内层为富Ni的Ni3Ti层．研究表明，Ti44Ni47Nb9合金中的Nb元素减少了TiO2中的氧空位，形成的富Nb阻挡层，能有效地抑制Ti元素的外扩散，同时也阻挡了氧的内扩散，降低了氧的固溶度，从而抑制了Ni3Ti层中Ni元素的进一步氧化，提高了合金的抗高温氧化性能．     

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.     

高Cr镍基单晶合金1050℃的高温氧化性能

采用X射线衍射(XRD)、扫描电镜(SEM)及能谱(EDAX)等手段,研究了一种高Cr镍基单晶高温合金在1050℃的高温氧化行为.结果表明,氧化初期合金增重迅速,氧化增重不遵循抛物线规律,表面氧化膜出现剥落,氧化过程由形成Al2O3和Cr2O3所控制.高温氧化期间,合金发生明显的外氧化和内氧化,外氧化膜Cr2O3和(Ni,Co)Cr2O4组成,内氧化物为Al2O3.在内氧化物上方出现贫Al富Ta区,元素贫化区尺寸随时间的延长而增大,富Ta相抑制基体中Al向外扩散,并抑制氧化膜生长.     

简单/改性铝化物涂层的研究现状

航空发动机各部件高温结构材料在苛刻环境下服役时,会遭受严重的高温氧化和热腐蚀.在合金表面施加铝化物涂层后,高温下表面能够生成一层致密且生长缓慢的Al2O3氧化膜,从而隔绝腐蚀介质,以防止合金被快速氧化腐蚀.概述了铝化物涂层的优点,包括制备简单、成本低廉.重点综述了以Ni、Fe、Ti/TiAl为合金基体的铝化物涂层微观结构.涂层的微观结构主要由渗铝工艺、基材成分及后处理工艺等因素决定,渗铝工艺包括渗剂成分、渗铝温度和渗铝时间.在高温下渗铝,Al的活度较低,涂层主要以基体元素向外扩散形成外扩散型涂层为主;在低温下渗铝,Al的活度较高,涂层主要以Al向内扩散形成内扩散型涂层为主.还归纳了不同渗铝涂层在干燥空气和水蒸气环境中的高温氧化行为,阐述了水蒸气对铝化物涂层高温氧化行为的影响,比较了Ni-Al系和Fe-Al系涂层的抗高温氧化性能.同时介绍了Cr-Al、Si-Al和Pt-Al 3种改性铝化物涂层的研究进展,包括制备方法、微观结构及抗高温氧化和腐蚀性能.最后,展望并总结了高温防护涂层的发展趋势.     

电弧离子镀NiCrAlYSi涂层抗高温氧化行为

采用电弧离子镀技术,在镍基高温合金DZ22B表面沉积一层NiCrAlYSi抗高温氧化涂层。利用SEM、XRD、EDS和电子探针等,分析了涂层的微观形貌、组织结构、物相和元素分布规律。研究了涂层和基体在1050℃的静态空气环境中恒温氧化200 h的氧化动力学规律和抗氧化性能。结果表明:沉积态涂层致密均匀,无孔洞等明显缺陷。经热处理后,涂层发生了β-NiAl向γ'-Ni_3Al的转变,主要物相为γ'-Ni_3Al/γ-Ni、β-NiAl和α-Cr相。恒温氧化200 h后,与基体相比,平均氧化速度由0.096 7g/(m~2·h)降到0.0340g/(m~2·h),显著提高了基体的抗高温氧化性能。氧化初期,涂层表面形成了一层均匀致密的α-Al_2O_3保护层,阻止氧向涂层内部扩散,从而大大提高了抗氧化性能。氧化过程中,涂层与基体的界面处发生了元素互扩散现象;主要为Cr元素从涂层向基体的内扩散和Co、W和Y元素从基体向涂层的外扩散。     

EFFECTS OF ACTIVE ELEMENTS Y AND Ce ON HIGH TEMPERATURE OXIDATION OF Fe-25Cr-40Ni ALLOY

The effects of small amount(≥0.05%)of active elements Y and Ce in Fe-25Cr-40Ni al-loy have been investigated on the kinetics of early stage of high temperature oxidationas well as composition and microsructure of oxide film by ion backscattering and slowpositron beam.The results show that Y and Ce can reduce evidently the high tem-perature oxidation rate of FeCrNi alloy at early stage and can effectively enhance theCr_2O_3 formation and retard the oxide formation of Fe and Ni in the surface layer thusthe microstructure of the oxide film is improved.Y and Ce enter the oxide film andconcentrate within several tens nanometres from surface of the outer layer.The mech-anism of oxidation resistance for Ce is different from Y.Ce can decrease the densityof vacancy defects in oxide layer,so the cations are restrained from diffusion outwardthrough vacancies.While Y can control the outward diffusion of cations through va-cancies at the early statge of oxidation(shorter than 12 min),aften that restrained thecations from diffusion outward along grain boundaries up to 60 min oxidation.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal

The oxidation behavior at 900°C of pure Cr and Cr implanted with 2×10¹⁶ Y ions/cm² was studied. The kinetics of oxidation were measured thermogravimetrically and manometrically. The mechanisms of oxide growth were studied using¹⁸O-tracer oxidation experiments, and the composition and microstructure of the oxide scales were characterized by TEM and STEM. Segregation of Y cations at Cr₂O₃ grain boundaries was found to be the critical factor governing changes in the oxidation behavior of Cr upon the addition of Y. In the absence of Y, pure Cr oxidized by the outward diffusion of cations via grain boundaries in the Cr₂O₃ scale. When Y was present at high concentration in the scale, as when Cr implanted with 2×10¹⁰ Y ions/cm² was oxidized, anion diffusion predominated. It is concluded that strain-induced segregation of Y at grain boundaries in the oxide reduced the cation flux along the grain boundaries. The rate of oxidation was reduced because the grain-boundary diffusivity of cations became lower than the grain-boundary diffusivity of the anions, which then controlled the rate of oxidation. Changes in the relative rates of Cr³⁺ and O^2– transport, as well as a solute-drag effect exerted by Y on the oxide grain boundaries, resulted in changes in the microstructure of the oxide.     

On the effects of surface coatings on the high-temperature oxidation of nickel

Ni and Ni coated with superficial oxide coatings including SiO₂, CeO₂ and La₂O₃ have been oxidized in the temperature range 500-1200 °C in 10⁻⁴-1 atm oxygen. The oxidation kinetics and the surface kinetics have been determined, and the microstructure and the composition of the oxide coatings and the thermally grown NiO scales have been characterized by a range of different microscopy and spectroscopy techniques. At 800-900 °C, the coatings decrease the oxidation rate by approximately one order of magnitude. The oxide coatings increase the relative growth inside the scale compared to uncoated Ni. Still, the major growth mechanism is governed by outward Ni diffusion, which indicates that the reason for the improved oxidation resistance is due to a decrease in the overall outward flux of Ni across the scales.     

On the High-Temperature Oxidation of Cu-Rich Cu-Ni Alloys

Cu-2 wt.%Ni and Cu-5wt.%Ni were oxidized at 800to 1050°C and oxygen pressures from from 5 ×10^-4 to 1 atm. The oxidation, as measured bythermogravimetry, was approximately parabolic. The oxidescales could be divided in two main regions: An outerregion consisting of copper oxides and an inner porousregion, which consists of Cu₂O with dispersedNiO particles. NiO particles exists as internal-oxide particles. The interface between the two layersreflects the original surface, which shows that theouter part grows by outward Cu diffusion via vacancies.The inner part grows by outward diffusion of copper and inward transport of gaseous oxygen by thedissociative-transport mechanism. The amount ofporosity, the relative thickness of the inner layercompared to the total thickness of the scale, and theoxidation rate as a function of Ni content was dependenton the reaction conditions.     

Nb对TiNiAl合金高温氧化行为的影响

对Ti50Ni44Al6和Ti50Ni41Al6Nb3合金在1073K循环氧化行为的测试表明，Nb的加入显著改善合金的高温抗氧化性能．Ti50Ni44Al6合金在1073K经过100h循环氧化后形成外层以TiO2为主并含有少量Al2NiO4、内层为TiNiO3的氧化层，合金的氧化动力学服从线性规律；Ti50Ni41Al6Nb3合金生成以TiO2为主的氧化膜，在外氧化层下面形成了一层富Nb和Al的复合氧化物，显著阻碍氧以及合金元素的扩散，降低了合金的氧化速率，合金高温氧化动力学遵从抛物线规律．     

Hf和Y对Ni3AI/CrMoB合金氧化性能影响

研究了Hf和Y对Ni3Al-7.8Cr-4Mo-0.05B合金氧化性能的影响,测定了合金在1000和1100℃的恒温氧化动力学曲线,并通过XRD分析表面氧化膜结构,通过扫描电镜和能谱分析研究了氧化产物的微观组织与成分.结果表明:Hf和Y的加入大大提高合金的抗氧化性能,主要影响在于形成稳定性更好的HfO2.提高氧化膜与基体的粘结力,抑制了硫在氧化皮/基体界面的偏聚、改变氧化膜的形貌与组成、内氧化程度、扩散层深度等.     

Internal Oxidation of Ternary Alloys Forming a High Oxygen Conductive Oxide

Five ternary alloys consisting of a noble base metal (Ni, Co, Fe, Cu) and two reactive metals (Zr + Y, Ce + Gd) being able to form a high oxygen ion conductive oxide were internally oxidized under low oxygen partial pressures. All alloys developed either a continuous yttria-stabilized zirconia phase or a continuous gadolinia-doped ceria phase behind the front of internal oxidation. A Ni–Ce–Gd alloy showed extraordinarily high internal oxidation rates of up to 120 µm²/s at 900 °C. High internal oxidation rates in these ternary alloys were not limited to low concentrations of the reactive metals. The type of the internal oxide phase was found to be more important for the internal oxidation kinetics than the noble base metal.     

Transition in the nanoporous structure of iron oxides during the oxidation of iron nanoparticles and nanowires

Changes in morphology during the oxidation of iron nanoparticles and nanowires in the temperature range 473–873 K have been studied by transmission electron microscopy. Iron nanoparticles and wires become hollow nanoparticles and nanotubes of magnetite at temperatures below 673 K as a result of vacancy aggregation during the oxidation process, resulting from the outward diffusion of iron ions through the magnetite layer. On the other hand, the hollow magnetite transforms into duplex porous structures with an interior nanopore and additional nanovoids at higher temperatures above 673 K, where the inner and outer diameters of magnetite nanotubes shrink and the phase transformation from magnetite to maghemite occurs. Transition in the porous structure seems to be related to the outward diffusion of vacancies from interior pore and the phase transformation from magnetite to maghemite.     

Evaluation of aluminide diffusion coatings for thermal cyclic oxidation protection of a nickel‐base superalloy

Active element modified aluminide diffusion coatings on IN738 substrates were produced by a new route using continuously cast, aluminum alloy wires consisting of Al‐Y, Al‐Ce, Al‐La and Al‐Si‐Y. The cast wires were used as evaporation sources for ion‐vapour deposition followed by diffusion heat treatments to form nickel aluminide coatings. In order to examine the oxidation resistance of these coatings at elevated temperatures, thermal cyclic oxidation experiments were carried out in air at 1050°C. While all coatings were found to provide significant protection, the Al‐La modified coatings provided the greatest resistance to cyclic oxidation. On the other hand, with coatings based on Al‐Si‐Y alloys, while silicon has a strong ability to reduce the outward diffusion of aluminum, the adverse effect of silicon on mechanical properties of the coating, together with the formation of volatile silicon monoxide, led to catastrophic localized oxidation of the protective coatings.