镧和铈对Fe25Cr5Al合金高温氧化行为的影响

含稀土元素La、Ce的Fe25Cr5Al-RE合金和不含稀土的Fe25Cr5Al合金在1100 ℃的空气中进行了恒温氧化实验。采用扫描电子显微镜（SEM）观察氧化膜形貌,使用X射线衍射仪（XRD）结合能谱仪（EDS）分析氧化膜成分。结果表明,氧化1、20和300 h后,Fe25Cr5Al合金增重分别为0.08、0.84和4.41 mg·cm^-2,Fe25Cr5Al-RE合金增重分别为0.03、0.35和0.92 mg·cm^-2。氧化后所有合金的氧化膜成分均为α-Al₂O₃。La、Ce能够促进合金形成致密、连续的氧化膜,显著提高了Fe25Cr5Al合金的抗高温氧化性能。此外,Fe25Cr5Al-RE合金氧化膜/基体界面存在稀土氧化物钉,使得氧化膜与基体的结合更加紧密,增强了氧化膜/基体粘附性。Fe25Cr5Al-RE合金氧化后,氧化膜内存在稀土氧化物,有效地防止了合金发生进一步氧化。     

不同Cr含量的Ni-Cr合金熔覆层的高温氧化和热腐蚀特性

采用激光熔覆技术制备了Cr质量分数为10%、20%和40%的Ni-Cr合金熔覆层,研究了其在900 ℃下的高温氧化特性和600 ℃下Na₂SO₄+25% K₂SO₄混合盐中热腐蚀特性。结果表明,Cr含量对熔覆层的高温特性起着关键作用。提高Cr含量对提升熔覆层抗硫酸盐诱导的热腐蚀能力比提升抗循环高温氧化能力更有效。Cr40涂层抗高温氧化和热腐蚀性能最佳。Cr10的氧化产物以NiO为主,极易脱落,内部氧化严重。虽然Cr40表面可以形成单一的Cr₂O₃层,但热应力和生长应力引起的富Cr氧化物内部开裂,使Cr40的抗循环高温氧化能力仅略好于Cr20。面对热腐蚀时,Cr10表面呈现层状NiO和Ni₃S₂叠层分布的腐蚀产物,内部腐蚀区也生成了Ni的硫化物。Cr20表面Cr₂O₃层被破坏,内部腐蚀严重,生成了CrS。Cr40表面生成了致密的Cr₂O₃保护层,有效地防止了进一步腐蚀。     

Co对铸态TiAl-Nb合金组织和高温氧化性能的影响

采用非自耗电弧熔炼方法经多次重熔制备了Ti45Al-6Nb-xCo合金(x=0, 0.5, 1, 2和4 at.%),研究了不同Co含量合金的组织结构和高温抗氧化性能。结果表明,增加合金中的Co含量能够细化α₂+γ片层组织,促进合金中形成γ和B₂相,并抑制α₂相形成;合金中Co含量超过2 at.%会导致富Co相析出和组织粗化。1000℃空气中的恒温氧化结果表明,适量的Co合金化能够显著改善TiAl-Nb合金的高温抗氧化性能;Ti45Al-6Nb-1Co合金的氧化的抛物线速率常数约为1.36×10^_-2mg^₂/cm^₄h,较Ti45Al-Nb合金低约1个数量级;但Co含量超过2 at.%后,随Co含量增加,合金的氧化速率呈增加趋势。     

氩弧熔敷原位合成TiC-TiB2/Ti基复合涂层组织及性能分析

利用氩弧熔敷技术,在TC4合金表面原位合成了TiC-TiB₂增强镍基复合材料涂层,利用SEM和XRD等方法分析了涂层的显微组织并测试了涂层的显微硬度.结果表明,熔敷组织主要由TiC,TiB₂和Ti(Ni,Cr)组成,TiB₂主要以棒状形式存在;在所形成的TiC-TiB₂/Ti复合材料层中,TiC和TiB₂颗粒分布均匀且尺寸细小;熔敷涂层由表及里组织不同;熔敷层与基体呈冶金结合,无气孔、裂纹等缺陷;涂层的显微硬度达到13.8 GPa,较基体提高了4.5倍.     

Si对625合金激光熔覆层高温氧化特性的影响

利用循环氧化法,研究了不同Si含量（0%,1%,3%,质量分数）的625合金熔覆层在700、800、900 ℃下氧化144 h后的高温氧化行为。用XRD分析了氧化物相。通过SEM/EDS研究了氧化物表面和截面的形貌、元素组成和氧化膜的厚度。结果表明,不同温度下试样的氧化动力学都保持抛物线规律,随着温度的升高,氧化增重逐渐增加。通过观察,在900 ℃时,0% Si含量的625合金熔覆层出现了氧化膜大面积剥落的情况,3% Si含量的合金熔覆层氧化膜保持完整。在700 ℃时,随着Si含量增加,氧化膜表面的氧化颗粒尺寸减小且更加致密,同时促进了Cr₂O₃氧化物的生成。在700 ℃下,0 % Si含量的试样出现了大片的内氧化区域;1% Si含量的试样基体部分出现了2处条状的含Ni,Cr,Mo的氧化物相区;而3% Si含量的试样氧化后由于生成了富Si的内氧化层,这阻止了内氧化的发生。外层Cr₂O₃氧化膜和内层SiO₂的联合作用既阻止了O阴离子的渗入也抑制了Fe等金属离子的扩散,提高了合金熔覆层的抗氧化性。     

超音速微粒沉积-激光同步强化Inconel718涂层高温氧化行为

针对镍基高温合金 Inconel 718 表面损伤问题,利用超音速微粒沉积-激光同步强化技术在基体表面制备了相同成分的 Inconel 718 修复涂层。 采用场发射扫描电子显微镜( SEM) 及其自带的能谱分析仪 EDS、X-射线衍射仪 (XRD)、显微拉曼光谱仪、场发射高分辨透射电子显微镜(TEM)分析了激光功率为 1300 W 时涂层的微观组织结构和 750 ℃高温氧化后表/ 截面形貌。 结果表明:涂层表面光洁,内部组织致密,孔隙率仅为 0. 2%,涂层与基体结合良好且无明显裂纹等缺陷。 在氧化初期,镍基高温合金涂层表面快速氧化并形成富 Ni、Fe、Cr 的 NiO、Fe₂O₃ 、Cr₂O₃ 以及含 Ni 的尖晶石 Cr₂O₃·NiO 结构。随着氧化时间的延长,NiO 与 Fe₂O₃ 结合生成复合相 NiFe₂O₄ ,而覆盖在 NiO 表面的 Cr₂O₃ 不断生长扩张,与 NiO 发生固相反应生成 NiCr₂O₄ 。     

TiAl合金表面Si-Co-Y扩散渗层的高温抗氧化性能

采用扩散共渗方法在TiAl合金表面制备了Si-Co-Y渗层,分析了渗层的组织结构、形成机理及其在950 ℃时的抗氧化性能。所制备的Si-Co-Y渗层组织致密,呈多层结构：主要由TiSi₂表层,TiSi₂+Ti₅Si₄+Ti₅Si₃混合组成的外层,Ti₅Si₃中间层和TiAl₂内层组成；渗层生长过程由Si的向内扩散控制,且遵循先沉积Si后沉积Co的有序过程。氧化实验结果表明,Si-Co-Y渗层具有良好的高温抗氧化性能,在950 ℃氧化100 h后表面形成了由SiO₂, TiO₂和Al₂O₃组成的保护性氧化膜；该氧化膜的生长遵循抛物线规律,氧化增重的抛物线速率常数约为6.3×10_-2 ^mg₂^/cm₄ ^h_1/2^,较基体合金低约一个数量级。     

EFFECT OF LaCoO3 COATING ON THE INTERMEDIATE TEMPERATURE OXIDATION BEHAVIOR OF SUS 430 METALLIC INTERCONNECT

通过溶胶--凝胶提拉法在SUS 430合金表面施加LaCoO₃钙钛矿导电涂层, 并研究其对固体氧化物燃料电池(SOFC)金属连接体SUS 430合金中温氧化行为的影响. 利用X射线衍射(XRD)、扫描电子显微镜(SEM)以及能谱仪(EDS)对施加涂层合金的氧化物相结构与微观形貌进行表征, 并采用“4点法”测量施加涂层合金表面氧化膜的面比电阻(ASR).750 ℃空气中的循环氧化结果表明, 施加LaCoO₃涂层合金的氧化动力学曲线遵循抛物线规律,氧化速率常数K为4.18×10^-15 g²/(cm⁴•s),比与未施加涂层合金降低了1---2个数量级;LaCoO₃涂层有效地抑制了Cr₂O₃相的形成, 减缓了MnCr₂O₄尖晶石的生长. 最终使得SUS 430合金的氧化抗力和氧化后的导电性得到增强.     

磁控溅射Cr/CrN和Cr/CrN/CrAlN涂层的抗高温氧化性能

为了提高航空紧固件涂层的高温工况防护能力,采用磁控溅射技术在钛合金表面分别制备 Cr/ CrN 交替涂层和 Cr/ CrN / CrAlN 涂层,研究氧化时间和氧化温度对涂层高温氧化性能影响。 利用 SEM、EDS 和 XRD 进行微观形貌和物相成分分析,采用热重法分析氧化增重量( w) 和氧化速率常数( k) ,使用显微硬度计测试涂层高温氧化后硬度。 结果表明:随着氧化时间和氧化温度的增加,涂层硬度均降低,但 Cr/ CrN / CrAlN 涂层下降趋势更缓; 两种涂层的 w 和 k 均上升,其中 Cr/ CrN / CrAlN 涂层 w 和 k 增幅均低于 Cr/ CrN 交替涂层,950 ℃ 氧化 96 h 后 Cr/ CrN / CrAlN 涂层和 Cr/ CrN 交替涂层的 w 值分别为 40 mg / cm ² 和 135. 7 mg / cm ² ,其对应的 k 分别为 0. 1996 和 0. 4092,说明 Cr/ CrN / CrAlN 涂层抗高温氧化性更好。 Cr/ CrN / CrAlN 涂层活化能 E_a 值比 Cr/ CrN 交替涂层高 48. 5%,Cr/ CrN / CrAlN 涂层在高温下产生 Cr₂O₃ 和 Al ₂O₃ 的混合氧化物,结构更致密,Cr/ CrN / CrAlN 涂层抗高温氧化性能高于 Cr/ CrN 交替涂层。     

La2O3含量对搅拌摩擦加工制备Ni /Al复合材料组织和性能的影响

采用搅拌摩擦加工方法在Al基体中添加不同La₂O₃含量的混合粉末(Ni+La₂O₃),制备 (Ni+La₂O₃)/Al复合材料。采用SEM、EDS、 EPMA及XRD对复合区微观结构及相组成进行分析,采用室温拉伸试验对 (Ni+La₂O₃)/Al复合材料力学性能进行了测试。结果表明,随着La₂O₃含量的增加,(Ni+La₂O₃)/Al复合材料的组织和性能先变好后变差。当La₂O₃添加量达到5%时,复合材料中Al₃Ni增强颗粒分布均匀、颗粒数量最多,块状的Ni粉团聚减少,其抗拉强度达到最大值215MPa,相比Ni/Al复合材料(抗拉强度176MPa),其抗拉强度提高了22%;当La₂O₃的添加量为7%时,复合材料中Al₃Ni增强颗粒含量减少,块状Ni粉团聚重新出现,抗拉强度下降至201MPa。     

The oxidation behaviour of austenitic FeCrNi alloys containing dispersed phases

The high temperature oxidation behaviour of FeCrNi austenitic alloys containing 1% Ti which, in some cases, had been converted into an oxide dispersion has been examined. The oxide dispersions were produced by an internal oxidation treatment using a 50/50 Cr/Cr₂O₃ powder mixture in a sealed quartz capsule at 1100°C: the samples were not in direct contact with the powders. Generally, the effect of the dispersed oxide was much less pronounced than in corresponding nickel-free, ferritic alloys. Nevertheless, the time-to-breakaway of the protective Cr₃O₃ scale which developed on Fe18CrNi alloys was substantially increased, although the differences between the untreated and the internally oxidized alloys reduced with increasing nickel content. An Fe14Cr20Ni alloy did not show any improvement after internal oxidation. Unlike the ferritic alloys, no coarsening of the dispersoid phase was observed during exposure.     

Ti含量对Ni-14Cr-10P-xTi焊膏连接C/C复合材料组织及性能的影响

将不同质量分数的钛粉加入Ni-14Cr-10P合金粉末中,再配合高分子聚合物制得膏状Ni-14Cr-10P-x Ti活性钎料,用制得的焊膏钎焊C/C复合材料,然后测试了钎焊接头的剪切强度,通过扫描电子显微镜、能谱分析仪、电子探针显微分析仪等对钎焊接头界面组织特征进行分析。结果表明:活性元素Cr、Ti与C/C复合材料表面的C反应而起到表面改性的作用,使得钎料能在C/C复合材料表面润湿、填缝。随着Ti元素加入量的增加,钎焊接头剪切强度先增加再降低。Ti质量分数为1%时,TiC呈颗粒状弥散分布,使得钎料层强化,接头剪切强度增加;当Ti增加到3%时,在界面处形成了连续的Cr_3C_2/TiC脆性材料层,接头剪切强度下降;Ti质量分数达到5%时,Ti与Cr_3C_2反应使得梯度界面层消失,界面物质热膨胀系数差异增大,残余热应力增加,同时Ti与Ni、Cr形成的金属间化合物增加并集中分布在钎料层中,导致接头剪切强度急剧下降。     

Effect of oxide grain structure on the high-temperature oxidation of Cr

Cr was oxidized in 1 aim O₂ at 980, 1090, and 1200°C. ElectropolishedCr and some orientations of etched Cr oxidize rapidly and develop compressive stress in the growing Cr₂O₃; other orientations oxidize slowly, apparently free of stress. SEM examination of fracture sections shows that the thick oxide is polycrystalline whereas the thin oxide on etched Cr is monocrystalline. It is deduced that the monocrystalline oxide grows by lattice diffusion of cations outward, and the polycrystalline layer by the two-way transport of cation diffusion outward and anion diffusion inward along oxide grain boundaries. The consequent formation of oxide within the body of the polycrystalline layer generates compressive stress and leads to wrinkling by plastic deformation. The activation energy for oxidation of Cr by cation lattice transport is 58 kcal/mole. Polycrystalline Cr₂O₃ forms on Fe-26Cr alloy, whether electropolished or etched; oxidation is accordingly rapid and accompanied by compressive stress.     

Optimization of Cr-Content for High-Temperature Oxidation Behavior of Co–Re–Si-Base Alloys

The oxidation behavior of Co-17Re-xCr-2Si alloys containing 23, 25, 27 and 30 at.% chromium at 1,000 and 1,100 °C were investigated. Alloy Co–17Re–23Cr–2Si showed a poor oxidation resistance during exposure to laboratory air forming a two-layer external scale and a very thin discontinuous Cr₂O₃ layer at the oxide/substrate interface. The outer layer of the oxide scale consisted of CoO, whereas the inner layer was a porous mixture of CoCr₂O₄ spinel particles in a CoO matrix. The oxide scale was found to be non-protective in nature as the vaporization of Re-oxide took place during oxidation. An increase of chromium content from 23 at.% to 25 at.% improved significantly the alloy oxidation resistance; a compact protective Cr₂O₃-scale formed and prevented the rhenium oxide evaporation. The oxidation behavior of alloys containing 27 at.% and 30 at.% chromium were quite similar to that of Co–17Re–25Cr–2Si. The oxidation mechanism for Co–17Re–25Cr–2Si alloy was established and the subsurface microstructural changes were investigated by means of EBSD characterization.     

The oxidation behaviour of cobalt-base alloys containing dispersed oxides formed by internal oxidation

CoCr alloys containing a dispersed oxide phase have been produced by internally oxidizing alloys to which 1 wt % of a reactive element—Hf, Ti or Zr—has been added. Internal oxidation was carried out in a sealed quartz capsule containing a 50/50 powder mixture of CrCr₂O₃, or X-40-Cr₂O₃. The alloys produced in this way show all the beneficial characteristics demonstrated by similar alloys made by other techniques: (a) a continuous protective Cr₂O₃ scale is established at a chromium level of 10%, considerably below that required (approximately 25%) in the absence of a dispersoid; (b) a reduction in the growth rate of the Cr₂O₃ compared to particle-free alloys, particularly at high temperatures, and (c) greatly improved adhesion of the protective scale to the substrate. The beneficial effects appear to be independent of the composition of the dispersoid, and also its distribution. Oxidation of the CoCr-1 Hf, Zr or Ti alloys without pre-treatment produces scales characteristic of the chromium content of a corresponding binary alloy, indicating that some internal oxidation treatment is necessary and it is not sufficient to rely on the internal oxides formed during normal oxidation.     

Oxidation Behaviour of NiCrAl and NiCoCrAl Bond Coatings Under Industrial Gas Turbine Conditions

Model bond coatings were deposited with a wide range of compositions and their oxidation behaviour investigated at 900 °C. These Ni–Co–Cr–Al coatings were deposited using magnetron sputtering (a physical vapour deposition technique) onto 10 mm diameter sapphire substrates. A range of compositions was generated by co-sputtering from a combination of two or three sources: Ni–10 wt% Cr, Ni–20Cr, Ni–50Cr, Ni–20Co–40Cr and/or Ni–40Co–20Cr combined with pure Al. The coatings were oxidised at 900 °C and the scales formed characterised. These data have been summarised into oxide predominance diagrams to show the relationships between coating compositions and the formation of protective Cr₂O₃ or Al₂O₃ scales, or the formation of other, less protective oxides (or mixed oxides). Both coating composition and exposure temperature (by comparison with earlier published research) were found to influence the oxide scale growth rate and oxide type, and thus the resulting degree of protection.     

Microstructural evolution,mechanical and thermal properties of TiC-ZrC-Cr3C2 composites

Dense TiC-ZrC-Cr₃C₂ composites with various TiC content from 19.6 mol% to 78.4 mol% have been fabricated by hot-pressing sintering at 1950 °C using 2.0 mol% Cr₃C₂ as sintering aid. The effect of TiC content on the microstructure, mechanical and thermal properties of TiC-ZrC-Cr₃C₂ composites are investigated systematically. The single (Zr, Ti, Cr)C solid solution is obtained when TiC content is 19.6 mol%, while with increasing TiC content, the composites begin to consist of Zr-rich (Zr, Ti)C solid solution and Ti-rich (Ti, Zr, Cr)C solid solution phase. SEM and EDS analysis confirm that Cr element is not favorable to diffuse into ZrC lattice to form (Zr, Cr)C solid solution. Flexural strength and Vickers hardness increase gradually with increasing TiC content, but fracture toughness does not improve significantly. Fracture toughness are in the range of 3.34–4.01 MPa∙m^1/2 for all composites, and the optimum value reaches 4.01 MPa·m^1/2 with 49.0 mol% TiC. Experimental results of the thermal expansion coefficient reveal that the addition of TiC raises the thermal expansivity of TiC-ZrC-Cr₃C₂ composites. Noticeably, the thermal conductivities of TiC-ZrC-Cr₃C₂ composites show a decrement trend with increasing TiC content, not as theoretical predicting by the rule of mixtures. For instance, the thermal conductivity at 25 °C ranges from 18.0 W/m∙K for 8Z2T2C composite down to 10.6 W/m∙K for 2Z8T2C composite.     

Beneficial Effects of Ce Implantation into Preformed Cr2O3 Scales on the Subsequent Oxidation of Ni–20Cr Alloy

The influence of Ce implantation into preformed Cr₂O₃ scales with a dose of 1 × 10¹⁷ ions/cm² on the subsequent oxidation behavior of Ni–20Cr alloy at 1050°C in air has been investigated. The pre-oxidation was carried out at 1050°C in air for 0.5 and 1 hr respectively Cr₂O₃ and NiCr₂O₄ formed on Ni–20Cr alloy. The oxidation rate was decreased remarkably due to Ce implantation regardless of whether it was implanted into the alloy or into the pre-formed oxide scales, and the beneficial effect decreased with increasing pre-oxidation time, the alloy implanted directly with Ce had the lowest oxidation rate constant. During cyclic oxidation (350 cycles) Ce implantation played a similar benefical effect on the oxide-spallation resistance for blank and pretreated alloys. The result indicates that Ce incorporated into the oxide scale affected the diffusion of the reaction species and also the spallation resistance of the oxide scales. The change of the oxidation process is attributed to the segregation of Ce at the oxide grain boundaries     

A review of the role of short-circuit diffusion in the oxidation of nickel,chromium, and nickel-chromium alloys

The evidence for short-circuit diffusion during the oxidation of nickel, chromium, and nickel-chromium alloys is reviewed. On the basis of experimental evidence for the Ni/NiO and Cr/Cr₂O₃ systems, inferences are made about the role of short-circuit diffusion through the oxide scales forming on the binary nickel-chromium alloys. The review highlights the importance of scale microstructure in governing oxidation rates.     

Relation between impurities and oxide-scale growth mechanisms on Ni-34Cr and Ni-20Cr alloys. I. Influence of C,Mn, and Si

The oxidation behavior of Ni-Cr alloys (34 and 20 wt.% Cr) was investigated between 850 and 1200°C in oxygen for a maximum duration of about 70 hr. The oxide-growth mechanism is a diffusion process controlled by either outward diffusion of chromium in Cr₂O₃ (Ni-34Cr alloy) or by an increase in grain size (Ni-20Cr alloy). In the case of the Ni-34Cr alloy, low values of chromium diffusion were found for the growth of Cr₂O₃ by taking into account the general equation of Wagner. The influence of impurities (Si, C, Mn, Ni) diffusing from the underlying alloy is analyzed because of their doping effect in the outer oxide scales.