DZ40M钴基合金低压气相沉积铝化物涂层的高温氧化相变

研究了ＤＺ４０Ｍ钴基合金低压气相沉积简单铝化物和钛改性铝化物２种涂层的形成及其高温氧化时的相变退化过程。     

Failure Behavior of an Aluminide Coating on a Co-Base Superalloy during High-Temperature Oxidation in Air

A surface-morphology change has been observed for an aluminide coating on the Co-base superalloy DZ40M during oxidation at 1100°C in air. The oxide formed on the coating remained an even grayish-white color during the stable oxidation stage, whereas, dark-colored corrosion nodules were observed when oxidation of the coating accelerated. The number of nodules increased with time, along with growth of the nodules, eventually covering the entire surface which signified failure.     

The Main Degradation Modes of an Aluminide Coating on a Co-Base Superalloy During High-Temperature Oxidation in Air

Degradation of aluminide coatings occurs by two ways, one by coating oxidation, and the other by interdiffusion of Al. In this paper, the structure variation and phase transformation are analyzed for the aluminide coating on a newly developed Co-base superalloy (DZ40M alloy) after oxidation at 900 and 1000°C in air. The results show that degradation of this coating was mainly by oxidation at 900°C, but principally by interdiffusion at 1000°C. The main degradation mode of the coating is primarily dependent on the oxidation temperature and the specific structure of the coating itself.     

Ti40合金的超高温氧化行为研究

对Ti40合金进行1000~1500℃的超高温氧化实验。应用SEM、OM、XRD和EDS分析氧化表面以及氧化表面到基体的组织和元素的变化。结果表明,Ti40合金在1000~1500℃氧化过程中,氧化表层分别经历了V2O5的熔化蒸发、TiO_2晶粒的长大,以及表面氧化层由于TiO_2的生长应力而导致的开裂剥落的过程。当氧化层脱落后,原有的氧化次表层推至氧化表面,形成致密的、具有较好保护作用的TiO_2和Cr_2O_3混和氧化层。同时,在氧化层和基体界面依然稳定存在V、Cr元素的富集层。TiO_2、Cr_2O_3混和氧化层和V、Cr元素的富集层使得氧化表层脱落后合金依然具有良好的抗O元素扩散能力。     

DZ40M钴基合金铝化物涂层的循环氧化

以新型定向凝固钴基高温合金ＤＺ４０Ｍ为基体,研究其低压化学气相沉积铝化物涂层的循环氧化行为,发现该涂层具有较高的抗循环氧化性能,涂层与基体结合良好。涂层退化主要是由外表面氧化膜的愈合消耗Ａｌ源所造成,沉积渗剂中加入Ｔｉ可加速涂层的退化。     

High-Temperature-Oxidation Behavior of Iron–Aluminide Diffusion Coatings

Aluminide diffusion coatings were oxidized in air under atmospheric pressure under isothermal and cyclic conditions. The high-temperature efficiency of the pack-aluminized alloys was tested by comparing their oxidation behavior in the temperature range 800–1080°C. The k _p values deduced from the parabolic plots of weight-gain curves showed that α-Al₂O₃ composed the major phase of the oxide scale on samples oxidized at T > 1000°C. For lower temperatures, transient-alumina phases were observed. The aluminide materials also exhibited excellent resistance to cyclic oxidation at 1000°C. The second aim of this study was to dope the aluminide compounds obtained by a pack-cementation process with yttria, which was introduced by metal-organic chemical-vapor deposition (MOCVD). The beneficial effect of the reactive-element-oxide coating is strongly dependent on its mode of introduction, since the oxidation resistance is drastically increased when the Y₂O₃ coating was applied prior to the aluminization process. When applied after the aluminization, the reactive element gave negative effects on the high-temperature oxidation behavior of the iron aluminides. The oxide morphologies, X-ray diffraction patterns and two-stage experiments helped to understand the oxide-scale-growth mechanisms.     

High-Temperature Oxidation Behavior of the Co-Base Superalloy DZ40M in Air

The oxidation behavior of the Co-base superalloy DZ40M was studied in air at900–1100°C for times of up to 2000 hr. The results indicated thatthis alloy can grow a protective oxide scale at 900 and 1000°C duringisothermal oxidation, but not at 1100°C because of serious cracking andspalling of the oxide scales. Moreover, an internal-precipitate zone formedin the subsurface region of the alloy at all temperatures and times. Theprecipitates were rich in Cr in the vicinity of the alloy–scaleinterface and rich in Al deep in the alloy. The internal-precipitatemorphology changed from a granular to needlelike shape with increasingoxidation temperature.     

Effect of Hf Additions on the Isothermal-Oxidation Behavior of TiAl at High Temperatures

The isothermal-oxidation behavior of TiAlcoupons containing Hf of up to 5.2 mass % has beenstudied in the temperature range 1100-1400 K in a flowof purified oxygen under atmospheric pressure. Theaddition of 0.2% Hf is very effective to decrease theoxidation rate at 1200 and 1300 K. Metallographicexamination using conventional methods revealed that theinitially-formed Al₂O₃ scale ismaintained very sound by the addition. However, further additions ofHf result in a slight enhancement of oxidation at 1200K and a gradual decrease of the effect at 1300 K.Finally, there is almost no effect by the addition of 5.2% Hf at 1300 K. Excess amounts of Hf leadto the formation of oxide mounds on theAl₂O₃ scale. They grow in size andnumber during subsequent oxidation until the wholespecimen surface is covered with a thick scale. Such a scale is notprotective having a structure often reported in theliterature. The effect of the addition of 0.2% Hfbecomes small at 1350 K and at 1400 K it is inverted.Possible mechanisms for the improvement attained by thesuitable addition are discussed.     

Y2O3 对DZ125合金表面Cr-Al-Y渗层的组织结构及抗氧化性能影响

为进一步提高DZ125合金高温服役性能,通过扩散渗方法在其表面制备了稀土元素Y改性的Cr-Al共渗层,研究了Y₂O₃含量对渗层组织结构及抗高温氧化性能的影响。结果表明：不同条件下制备的Cr-Al-Y渗层均具有三层结构,由外向内依次为：Cr+Ni₃Cr₂外层,Ni₃Cr₂+Al₁₃Co₄中间层,以及Ni₃Al内层。当渗剂中Y₂O₃含量为0%～2%(质量分数,下同)时,渗层的厚度与密度显著增加;当稀土Y₂O₃的添加量过高时(5%),渗层的密度及厚度反而下降。1100℃高温氧化实验表明,Cr-Al-Y渗层显著提高了DZ125合金的抗高温氧化性能。     

Changes of an Outer β-NiAl and Inner α-Cr Coating on Ni–40 at% Cr Alloy during Oxidation at 1373K in Air

Formation mechanisms of a coating with a duplex layer, outer β-NiAl(Cr) and inner α-Cr(Ni) layer structure on a Ni–40.2 at% Cr alloy were proposed and change in the coating structure was investigated during high temperature oxidation. The Ni–40.2 at% Cr alloy was electro-plated with about 12μm Ni followed by a high Al activity pack cementation at 1073K to form a coated layer with an outer δ-Ni₂Al₃ and an inner layer containing Al more than 70at% which grew with an inward diffusion of Al. The coated Ni–40.2at% Cr alloy was oxidized at 1373K in air for up to 2592ks. It was found that at the initial stage of oxidation the as-coated layer structure changed to a two-layer, outer β-NiAl(Cr) and inner α-Cr(Ni), structure. Al contents in the α-Cr(Ni) layer was less than 0.3at%. With long term oxidation an intermediate γ-Ni(Cr, Al) layer formed between the outer and inner layers, whereas the inner α-Cr(Ni) layer became thinner and then disappeared after the 2592ks oxidation at 1373K. Coating processes and changes in the coating structure during high temperature oxidation were discussed based on diffusion and composition paths plotted on a Ni–Cr–Al phase diagram     

High-Temperature Oxidation of an Aluminized NiCr Alloy formed by a Magnetron-Sputtered Al Diffusion Coating

Aluminium diffusion coatings were obtained on Ni–20Cr substrate by sputtering an aluminium film, followed by a two stage diffusion treatment in an argon inert gas atmosphere (first stage at 600°C, second at 900 or 1100°C). Aluminides obtained at 900°C and 1100°C are close to those obtained by pack cementation process with high aluminium activity. These diffusion coatings are able to develop alumina scales during isothermal oxidation at high temperatures, whereas the untreated substrate had a chromia-forming behaviour. The weight gain recorded at 1100°C on coated sample is then smaller than the one of uncoated NiCr at 950°C. Presence of chromium was detected in the diffusion coating and Cr-rich precipitates were observed at the diffusion coating/substrate interface. After oxidation at 900°C and 1100°C, only α-Al₂O₃ was revealed by XRD. An intermediate scale with a “whiskered” morphology could however be observed after 48 hr oxidation at 900°C. After 100 hr of oxidation at 1100°C, the Ni_xAl_y diffusion phases were no longer detectable and the upper part of the oxide scale spalled away during cooling. Large cavities appeared at the initial location of the diffusion coating/substrate interface.     

Effect of Micro Arc Oxidation Coatings on Corrosion Resistance of 6061-Al Alloy

In the present study, the corrosion behavior of micro arc oxidation (MAO) coatings deposited at two current densities on 6061-Al alloy has been investigated. Corrosion in particular, simple immersion, and potentiodynamic polarization tests have been carried out in 3.5% NaCl in order to evaluate the corrosion resistance of MAO coatings. The long duration (up to 600 h) immersion tests of coated samples illustrated negligible change in weight as compared to uncoated alloy. The anodic polarization curves were found to exhibit substantially lower corrosion current and more positive corrosion potential for MAO-coated specimens as compared to the uncoated alloy. The electrochemical response was also compared with SS-316 and the hard anodized coatings. The results indicate that the overall corrosion resistance of the MAO coatings is significantly superior as compared to SS316 and comparable to hard anodized coating deposited on 6061 Al alloy.     

不同表面粗糙度镍铬铝合金的高温氧化行为

采用热重法并结合X射线衍射、扫描电子显微镜、能谱仪等分析手段,研究在1000 ℃条件下Ni-10Cr-5Al (质量分数,%) 合金样品表面粗糙度对其氧化行为的影响。结果表明：经1000 ℃氧化215 h后,不同表面粗糙度的合金其氧化动力学均服从抛物线规律,并存在两个抛物线常数,氧化膜主要由Al₂O₃,NiCr₂O₄和NiAl₂O₄组成。随着表面粗糙度的增加,氧化增重越明显,同时氧化膜脱落越严重、氧化膜金属界面越起伏。其中,表面粗糙度对合金氧化的影响主要是在氧化前期阶段促进生成了尖晶石NiCr₂O₄和NiAl₂O₄氧化物。     

Al2O3微粉添加量对镁合金微弧氧化膜特性影响研究

为了研究添加Al₂O₃微粉对AZ31A镁合金微弧氧化膜特性影响,在不同浓度Al₂O₃微粉电解液中对其进行了微弧氧化处理。利用扫描电镜(SEM)观察微弧氧化膜形貌,能谱仪(EDS)分析了膜层表面Ca、Mg、O、Al元素分布,X射线衍射仪(XRD)分析了相组成,测定了膜厚、硬度和氧化液中Al₂O₃表面电荷,讨论了掺杂改性机理。结果表明,加入Al₂O₃微粉后,氧化电压随Al₂O₃添加量增加先增加后降低;氧化膜表面孔洞数量和尺寸减小,膜层表面Ca元素分布逐渐减少,成膜效率降低,膜层致密度和表面疏松层硬度提高,氧化膜主要由MgO和MgO₄等相组成。     

Effect of Palladium Incorporation on Isothermal Oxidation Behavior of Aluminide Coatings

A (Ni, Pd)Al coating has been prepared by low-pressure pack cementation on the nickel-base superalloy IN738 with a preplating of Pd–20 wt.% Ni alloy. The coating consists mainly of a single phase of -Pd(Ni)Al in the outer part and -Ni(Pd)Al in the inner part. The oxidation behavior of the (Ni,Pd)Al coating at 900–1100°C was studied by TGA, XRD, and SEM/EDS. Results show that the transformation of - to -Al₂O₃ is more rapid on the (Ni,Pd)Al coating than that on a simple NiAl coating. The addition of Pd to the aluminide coating facilitates the transformation of - to -Al₂O₃e oxide scale formed and accelerates the diffusion of Ti from the substrate to the coating surface simultaneously.     

钛合金表面抗高温氧化涂层的研究进展

钛合金在制造航空航天发动机等关键部件方面具有重要的应用价值,但高温性能不稳定是制约其发展前景的主要原因。采用激光熔覆技术在钛合金表面制备耐高温涂层,是在不改变钛合金材料整体性能的前提下赋予材料表面特殊性能的重要途径。首先介绍了钛合金的氧化行为,并简要分析了钛合金在氧化过程中的氧化特点及失效形式,指明其改善途径。随后总结分析了目前常用的镍基高温涂层、TiAl系高温涂层和高熵合金高温涂层的研究现状,其中镍基合金涂层具有较高的结合强度、良好的耐磨性和优异的耐蚀性,但由于涂层与基体中元素的扩散速率不同导致的差异,造成柯肯达尔空洞的产生,涂层变得不稳定,涂层与基体的结合强度降低。TiAl基合金的高温性能与镍基高温合金相近,且密度小,有代替镍基合金的发展趋势,其涂层表面可以生成均匀致密的Al2O3氧化膜,并且与钛合金基体间的化学成分差异小,基本不发生互扩散现象。但二元TiAl系涂层对于Al的用量有严格的要求,当其使用温度超过850 ℃时,抗氧化性能也会严重降低。因此Ti-Al-X系涂层中X元素（例如Cr、Si、Ni等元素）的添加,可以适当地降低Al含量,促进均匀致密的Al2O3氧化膜的形成,有效地阻止氧元素向基体的扩散,并且比二元TiAl涂层的脆性要低、塑性更好。高熵合金高温涂层具有许多优异的性能,调整其中某一种或者某几种元素的含量都可以进一步优化性能,因此应用前景极为广阔,但其还处于实验室研究阶段,元素配比的不合理,基体元素对熔覆层的反作用,都会使高熵合金的脆性和力学性能达不到理论效果,不能进入真正的应用阶段。最后展望了激光熔覆技术在钛合金表面制备高温涂层的发展趋势。     

Oxidation resistance of refractory γ-TiAlW coatings

The resistance to oxidation of the W-alloyed magnetron sputtered γ-TiAl fine-crystalline 4 μm thick coatings have were investigated in this work. The oxidation tests were performed in an atmosphere of pure oxygen or in the air at a temperature of 1173 K for 120 h. The resistance to high-temperature oxidation was investigated by means of micro-thermogravimetric analysis with continuous or stepwise control of the substrate weight. Before and after the oxidation the morphology of the coatings as well as their chemical and phase composition were investigated by SEM, EDS and EBSD, respectively. The results have been compared with those obtained for the uncoated γ-TiAl substrate.It was found that: (1) the W-alloyed γ-TiAl coatings have a considerably higher oxidation resistance (about four orders of magnitude) than the uncoated γ-TiAl substrates and that their resistance to oxidation increases with the concentration of alloying element in the range of the concentrations investigated in the work; (2) the high resistance to oxidation of the coatings is a result of the thin α-Al₂O₃ layer formation on the surface of the substrate during oxidation; (3) the formation of dense and uniform α-Al₂O₃ layer on the coating surface is due to a fine-crystalline structure of the magnetron deposited γ-TiAlW coating.     

Substrate Effect on the High Temperature Oxidation Behavior of a Pt-modified Aluminide Coating. Part II: Long-term Cyclic-oxidation Tests at 1,050 °C

This second part of a two-part study is devoted to the effect of the substrate on the long-term, cyclic-oxidation behavior at 1,050 °C of RT22 industrial coating deposited on three Ni-base superalloys (CMSX-4, SCB, and IN792). Cyclic-oxidation tests at 1,050 °C were performed for up to 58 cycles of 300 h (i.e., 17,400 h of heating at 1,050 °C). For such test conditions, interdiffusion between the coating and its substrate plays a larger role in the damage process of the system than during isothermal tests at 900, 1,050, and 1,150 °C for 100 h and cyclic-oxidation tests at 900 °C which were reported in part I [N. Vialas and D. Monceau, Oxidation of Metals 66, 155 (2006)]. The results reported in the present paper show that interdiffusion has an important effect on long-term, cyclic-oxidation resistance, so that clear differences can be observed between different superalloys protected with the same aluminide coating. Net-mass-change (NMC) curves show the better cyclic-oxidation behavior of the RT22/IN792 system whereas uncoated CMSX-4 has the best cyclic-oxidation resistance among the three superalloys studied. The importance of the interactions between the superalloy substrate and its coating is then demonstrated. The effect of the substrate on cyclic-oxidation behavior is related to the extent of oxide scale spalling and to the evolution of microstructural features of the coatings tested. SEM examinations of coating surfaces and cross sections show that spalling on RT22/CMSX-4 and RT22/SCB was favored by the presence of deep voids localized at the coating/oxide interface. Some of these voids can act as nucleation sites for scale spallation. The formation of such interfacial voids was always observed when the β to γ′ transformation leads to the formation of a two-phase β/γ′ layer in contact with the alumina scale. On the contrary, no voids were observed in RT22/IN792, since this β to γ′ transformation occurs gradually by an inward transformation of β leading to the formation of a continuous layer of γ′ phase, parallel to the metal/scale interface.     

铂含量对改性铝化物粘结层高温氧化和内应力的影响

研究镍基高温合金的热障涂层系统中不同铂含量的改性铝化物粘结层在1100℃空气中循环氧化和非连续氧化行为及生成的氧化铝层的内应力状态。发现在不同循环氧化条件下,铂铝粘结层表面都形成连续致密的α-Al2O3层,并且α-Al2O3具有相同的形态和相似的平均厚度。而在非连续氧化初期,Al2O3层热生长应力快速增大,在氧化至100h时内应力出现峰值。同时由于高含量铂促进Al元素的扩散从而改变了涂层力学性能,造成高含量铂涂层中表现较大的内应力,但铂含量不能影响Al2O3层中内应力曲线变化趋势。另外,低铂含量涂层γ′-Ni3Al多沿β-NiAl晶界生成,而高含量铂使涂层晶粒细化,导致γ′-Ni3Al相呈弥散分布生长,从而可以形成Al元素的"网"状快速扩散通道。     

铌合金表面高温抗氧化涂层

介绍了铌合金表面高温抗氧化涂层的4大体系——耐热合金涂层、铝化物涂层、硅化物涂层和贵金属涂层的组成、特点及制备条件。我国研究人员围绕飞机发动机涡轮叶片和火箭发动机燃烧室及尾气喷管用铌合金的防护进行了大量研究工作，研制的高温抗氧化涂层已经用于49kN推力发动机铌合围裙和姿态控制铌合金喷管。通过研究认为，PVD和传统熔烧工艺相结合的新工艺及纳米涂层技术是今后铌合金表面高温涂层制备的研究方向。