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。     

CoCrNiAlY涂层制备工艺对组织形态及高温氧化行为的影响

为了研究CoCrNiAlY涂层微观组织结构对高温氧化行为和剥落行为的影响规律,采用激光熔覆技术和等离子喷涂工艺在718高温合金表面制备CoCrNiAlY涂层,观察其微观组织形态。利用XRD和SEM对1150 ℃高温氧化试验样品进行氧化层物相分析和形貌观察。结果表明,激光熔覆制备的CoCrNiAlY涂层中形成了胞状亚结构的等轴晶凝固组织,相对于等离子喷涂制备的CoCrNiAlY涂层结构更致密,具有更优异的抗高温氧化性能。在高温氧化过程中,等离子喷涂CoCrNiAlY涂层生成了以Cr₂O₃结构为主的复合氧化膜。激光熔覆CoCrNiAlY涂层生成Al₂O₃结构的单一氧化膜,而且熔覆层中原位形成的Y₂O₃钉扎作用能有效提高氧化膜的抗剥落性。文中系统分析讨论了两种不同工艺制备的组织形态对高温氧化膜形成机制的影响,激光熔覆涂层在高温下主要是以界面扩散方式形成致密的Al₂O₃膜,等离子喷涂涂层在高温下以界面反应的方式快速形成Cr₂O₃复合氧化膜。     

成分设计优化TiC/Hastelloy复合材料的抗氧化性能

TiC/Hastelloy复合材料是极具应用前景的中温固体氧化物燃料电池连接体材料,而抗氧化性能是影响其应用的关键性能之一。通过无压反应渗透工艺分别制备出含有50vol%和58vol%金属基体的TiC/Hastelloy复合材料。高金属含量使复合材料中的Cr含量增加,促进连续Cr₂O₃氧化层的形成,抑制Ni和Ti原子的外扩散,进而优化复合材料的抗氧化性能。氧化膜中Ti和Ni的氧化物含量降低,复合材料的氧化增重由2.03 mg·cm^-2降低到0.55 mg·cm^-2。同时,为了抑制Cr挥发,在含有58vol%金属基体的TiC/Hastelloy复合材料中引入Co。在氧化过程中,Co和金属基体中的Fe在Cr₂O₃氧化层中具有较快的扩散速率,可以在Cr₂O₃氧化层外侧原位形成CoFe₂O₄层。     

稀土改性Fe-Al层表面Al2O3 薄膜的物相分布

在760 ℃下采用稀土改性包埋渗铝以及原位氧化方法制备Fe-Al/Al₂O₃复合涂层,研究了渗铝层和氧化膜的微观组织和相分布。结果表明,稀土改性渗铝层可分为3层：外层渗铝层、过渡层和内扩散层。渗铝层主要由FeAl相和Fe₃Al相组成。FeAl相主要集中在渗铝层的外层,为Al₂O₃氧化膜的选择性氧化提供了有利条件。氧化膜表面呈α-Al₂O₃脊状结构。此外,表面氧化铈的存在是由于氧化初期Ce向外扩散且与O₂的优先反应。氧化膜可分为2层,即纯α-Al₂O₃层和主要由α-Fe(Al)和Al、Fe、Ce的混合氧化物组成的过渡层。     

低氧压预氧化对FeCrAlSiY合金耐LBE熔液腐蚀性能的影响

为进一步提高核反应堆系统的结构材料 Fe-Cr 基合金抗 LBE 腐蚀的性能,对其进行成分优化和表面处理十分重要。 对 Fe-12Cr-xAl-2Si-0.6Y 合金进行低氧压预氧化试验,分析并讨论氧分压和 Al 含量对合金预氧化产物的影响,并研究预氧化前后的合金在 LBE 合金熔液中的耐腐蚀性能。结果表明,Fe-12Cr-2Al-2Si-0.6Y 合金在不同氧分压下进行预氧化后生成的表面氧化物均以 Al2O3 为主,氧分压越大,合金表面发生选择性氧化速度越快。不同 Al 含量的 Fe-12Cr-xAl-2Si-0.6Y 合金在 10^?15 atm(1 atm=0.101 3 MPa)氧分压下进行预氧化,随着 Al 含量的增加,合金表面氧化物由以 Cr₂O₃为主逐渐变为以 Al₂O₃ 为主,还混合有少量复合氧化物。进行低氧压预氧化处理能有效提高合金在 450 o C 的 LBE 合金熔液中的耐腐蚀性能。研究成果可为设计和开发耐 LBE 熔液腐蚀的 FeCrAlSiY 合金提供参考,促进该体系合金在核电工业领域的运用。     

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。     

BT25Y钛合金在600 ℃—800 ℃的高温氧化行为研究

研究了BT25Y钛合金在600 ℃、700 ℃和800 ℃下的高温氧化行为。采用连续氧化增重法,并结合氧化速度常数、氧化活度等理论计算了合金的氧化动力学和热力学规律;利用XRD、SEM和EDS等表征方法研究了氧化膜的相结构和表面、截面形貌及元素分布。结果表明：BT25Y钛合金在600 ℃和700 ℃均有较好的抗氧化性能,其连续氧化动力学曲线符合抛物线规律,氧化层由细小TiO₂和Al₂O₃组成,氧化膜可有效阻止氧渗入基体,降低氧化速度;BT25Y钛合金在800 ℃氧化严重,其连续氧化动力学曲线近似符合直线规律,氧化层由Al₂O₃层和TiO₂层交替组成,氧化膜疏松多孔,不能有效阻挡氧向基体一侧的扩散。     

FB3-F银钎剂去膜机理

研究了由H₃BO₃、K₂B₄O₇和KF（质量比为7:10:3）3种组分配制而成的银钎剂的去膜机理。结果表明：在700 ℃时,K₂B₄O₇或KF都不能单独去除Q235钢板表面的氧化膜,且KF会加快高温下钢表面的氧化速率;H₃BO₃能够去除Q235钢表面的氧化膜,然而其反应产物具有明显的非晶结构特征,并且流动性差。此外在700 ℃时,H₃BO₃与KF能够发生反应,其反应产物可以去除钢表面氧化膜。KF和K₂B₄O₇之间也能在700 ℃发生类似的反应,然而其反应产物非常坚硬。因此,在700 ℃时,H₃BO₃、K₂B₄O₇和KF混合钎剂能够与Q235钢板表面氧化膜反应,且反应产物具有明显的非晶特征。KF的加入将非反应性H₃BO₃-K₂B₄O₇二元体系转化为反应性KF-H₃BO₃-K₂B₄O₇三元体系。在这个三元体系中,KF不但对钢板没有腐蚀性,反而促进了氧化膜的去除。     

粉末包埋渗铝与气氛渗铝对P92钢650℃饱和蒸汽氧化行为的影响

表面渗铝技术可以在不改变基体材料力学性能的基础上显著提高基体的抗高温蒸汽氧化性能。 利用低温粉末包埋和气氛渗铝两种方法在 P92 钢表面制备了铝化物涂层,并结合氧化增重法、扫描电镜观察及 XRD 分析,研究了两种工艺下铝化物涂层的 650 ℃饱和蒸汽氧化行为。 结果表明:P92 钢抗氧化能力不足,生成了由外层疏松层瘤状富铁氧化物与表面氧化膜下方内氧化物 FeCr₂O₄ 组成的双层结构氧化膜,外层富铁氧化膜在氧化 300 h 后发生剥落;低温包埋渗铝所得涂层为 β-FeAl 层,氧化 500 h 后试样表面形成极薄的保护性 α-Al₂O₃ 氧化膜(<0. 2 μm);气氛渗铝涂层为单层 Fe₃Al 结构,氧化 500 h 后试样外表面形成了 Fe₃O₄₊Fe₂O₃ 氧化膜,厚度为 1. 3 μm,靠近涂层表面生成单层连续 Al₂O₃ 氧化膜。 采用低温包埋和气氛渗铝均可提升 P92 钢的抗蒸汽氧化能力。     

Si对Ni-Cr-Mo合金熔覆层高温耐腐蚀性能的影响

为研究Si含量对Ni-Cr-Mo系合金熔覆层耐高温腐蚀性能的影响，利用激光熔覆技术制备了4种不同Si含量的熔覆层。采用失重法测试了4种熔覆层在模拟垃圾发电腐蚀环境中多种温度下的耐腐蚀性能。通过对4种熔覆层在600及650℃下腐蚀产物的特性分析，发现Si的加入有助于腐蚀产物中富Cr氧化皮的稳定性。还可以通过“钉扎”作用提升富Cr氧化皮与基体的粘结性，从而有效提高熔覆层的耐腐蚀性能。但Si含量并非越多越好。当温度提升到600℃以上，含3%(质量分数，下同)Si的合金展现了最佳的耐腐蚀性能。这是由于含3%Si的合金腐蚀层中形成了一层保护性的SiO₂，有助于耐腐蚀性能的提升。而含1%Si的合金由于Si含量较低，含5%Si的合金由于Si的偏析严重，均未能形成有效的SiO₂保护层。     

两种铸造镍基合金的高温氧化行为

利用热重分析法、XRD和SEM (EDS)对比研究了700℃超超临界发电机组用K317和K325铸造合金在900和1000℃大气环境下氧化行为。结果表明,K317的氧化性能要优于K325。在900℃氧化时,2种合金的氧化增重遵循抛物线规律,而在1000℃氧化时,氧化增重均分段遵循抛物线规律。K317的氧化膜分3层,外层是NiO、TiO_2和NiCr_2O_4,中间层是致密的Cr_2O_3,内层是内氧化产物Al_2O_3。而K325的氧化膜分2层,外层是NiO, NiCr_2O_4和Nb_2O_5,内层是致密的Cr_2O_3和嵌入的Nb_2O_5颗粒,没有内氧化现象发生。在1000℃氧化时,K325中的Mo严重被氧化形成挥发性MoO_3;同时氧化膜发生了局部剥落现象,氧化膜的附着性相对较差。     

The Isothermal and Cyclic Oxidation Behavior of a Titanium Aluminide Alloy at Elevated Temperature

The isothermal and cyclic oxidation behavior of Ti-47Al-2Mn-2Nb with 0.8 vol.% TiB₂ particle-reinforced alloy was investigated in air between 700 and 1000 °C. In the study, the kinetics of isothermal and cyclic oxidation were performed by using a continuous thermogravimetric method which permits mass change measurement under oxidation conditions. The oxide scales and substrates were characterized by scanning electron microscopy with energy-dispersive x-ray analysis and x-ray diffraction. At 700 and 800 °C, the alloy showed an excellent oxidation resistance under isothermal and cyclic conditions. After exposure to air above 800 °C, the outer scale of the alloy was dominated by a fast-growing TiO₂ layer. Under the coarse-grained TiO₂ layer was the Al₂O₃-rich scale, which was fine-grained. At 900 and 1000 °C, the extent of oxidation increased clearly. The oxidation rate follows a parabolic law at 700 and 800 °C. However, the alloy, upon isothermal oxidation at 900 °C, can be divided into several stages. During the cyclic oxidation at 900 and 1000 °C, partial scale spallation takes place, leading to a stepwise mass change.     

Establishing multilayered coating on Mo–12Si–8.5 B alloy by Si pack cementation and its oxidation behavior at 900°C–1300°C

A multilayered oxidation protection coating consisting of MoSi₂ outer layer, Mo₅Si₃ internal layer, and Mo₅SiB₂/MoB inner layer was developed on the surface of Mo–12Si–8.5B 1.0 wt% ZrB₂ alloy via Si pack cementation. The multilayered coating significantly enhanced the oxidation resistance of the alloy at 900°C, 1100°C, and 1300°C in the air by exhibiting negligible oxidation recession. MoSi₂ outer layer provided admirable oxidation protection for the alloy at high temperatures by forming a thin and protective SiO₂-rich glass scale on its surface. This was supplemented by the Mo₅Si₃ internal layer and Mo₅SiB₂/MoB inner layer that reduced the thermal expansion mismatch between the MoSi₂ outer layer and substrate, and therefore no obvious cracks were found in the MoSi₂ outer layer. More importantly, the Mo₅SiB₂/MoB layer as an in situ barriers of Si interdiffusion ensured the stable existence of MoSi₂ and Mo₅Si₃ layers without obvious thickness change during oxidation at 900°C and 1100°C. Mechanical property test indicated that the formation of the coating layers could not affect the fracture toughness of the alloy.     

High-Temperature Corrosion Behaviour of Aluminized-Coated and Uncoated Alloy 718 Under Cyclic Oxidation and Corrosion in NaCl Vapour at 750 °C

To evaluate the suitability of HR3C and 22Cr–25Ni–2.5Al AFA steels as the heat-resistant alloys, the oxidation behavior of them was investigated in air at 700, 800, 900 and 1000 °C. The evolution of oxide layer on the surface and subsurface was investigated using a combination of compositional/elemental (SEM, EDS) and structural (XRD, GDOES) techniques. A dense and continuous Cr₂O₃ healing layer on the HR3C was formed at the temperature of 700 or 800 °C, but the Cr₂O₃ oxide film on HR3C was unstable and partly converted into a less protective MnCr₂O₄ with the increase in temperature to 900 or 1000 °C. The composition and structure of oxide film of 22Cr–25Ni–2.5Al AFA steels are significantly different to the HR3C alloys. The outer layer oxides transformed from Cr₂O₃ to Al-containing oxides, leading to a better oxidation resistance at 700 or 800 °C compared to HR3C. Further, the oxide films consist of internal Al₂O₃ and AlN underneath the outer loose layer after 22Cr–25Ni–2.5Al AFA oxidized at 900 or 1000 °C. It can be proved that the internal oxidation and nitrogen would make 22Cr–25Ni–2.5Al AFA steels have worse oxidation resistance than HR3C alloys at 900 or 1000 °C.     

低氧分压下NiTi记忆合金氧化行为的研究

本文研究了NiTi形状记忆合金在H₂-H₂O气氛下400-700 °C的氧化行为。合金的氧化过程遵循立方规律,氧化激活能127.52 kJ/mol。氧化显著降低了试样表面的Ni含量。400 °C氧化的试样,其表面形貌与其他试样不同,并且氧化膜较薄,截面结构无法用SEM分析。500 °C、600 °C、700 °C氧化的试样,表面有两种形貌的氧化物,一种是颗粒状氧化物,另一种是晶须状氧化物。截面分析表明,氧化膜分为两层,上层由TiO₂构成,下层由Ni₃Ti构成,两层界面处有孔洞生成。     

Characterisation of oxide films formed on Co–29Cr–6Mo alloy used in die-casting moulds for aluminium

Oxide films formed at 700 °C on Co–29Cr–6Mo alloy were characterised extensively to improve the corrosion resistance of the alloy to liquid Al, enabling its use in Al die-casting moulds. Film of duplex layer consisting of an outer CoO-rich layer and an inner Cr₂O₃-rich layer was observed in samples subjected to oxidation for 4 h. With an increase in duration of oxidation, CoO was gradually replaced by Cr₂O₃, resulting in a single-layered oxide film dominantly composed of Cr₂O₃. The oxide film evolved with duration of oxidation treatment indicating the possibility of optimising films for Al die-casting moulds.     

Oxidation behaviour of Nimonic 263 in high-temperature supercritical water

The oxidation tests of the Nimonic 263 alloy exposed to deaerated supercritical water at 600–700°C under 25?MPa were carried out for up to 1000?h. Oxidation rate increased with an increase in temperature. The microstructure and phase composition of oxide scale were analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It can be seen that a complex oxide structure formed on the surface of Nimonic 263 including an outer layer of Ni–Fe/Ni–Cr spinel oxide, Ni/Co hydroxide and TiO₂ and an inner layer of a mixture of NiCr₂O₄ and Cr₂O₃ while the innermost layer is made up of Cr₂O₃. The MoO₃ can be observed at 600°C but disappeared with the increasing temperature. The growth mechanism of oxide scale was discussed.     

Roles of Nb on the oxidation characteristics and oxide scale evolution of Fe-25Cr-35Ni-2.5Al-XNb alloys at 1000°C and 1100°C

The oxidation characteristics of Fe-25Cr-35Ni-2.5Al-_XNb (0, 0.6, and 1.2 wt%) alumina-forming austenitic alloys at 1000°C and 1100°C in air were investigated. Results show that Nb has an important effect on the high-temperature oxidation resistance. A bilayer oxide scale with a Cr₂O₃-rich outer layer and Al₂O₃-rich internal layer forms on the surface of the Nb-free alloy and exhibits a poor oxidation resistance at 1000°C and 1100°C. With Nb addition, both the 0.6Nb-addition and 1.2Nb-addition alloys exhibit better oxidation resistance at 1000°C. Because of the third element effect, Nb addition reduces the critical Al content and forms a single external protective Al₂O₃ scale, which greatly improves the oxidation resistance. After oxidation at 1100°C, niobium oxides (mainly Nb₂O₅) are formed on the surface of the 1.2Nb-addition alloy and destroy the integrity of the Al₂O₃ scale, which causes the formation of Cr-rich oxide nodules and eventually develops to be a loose bilayer oxide scale with NiCr₂O₄, Cr₂O₃, and Fe₂O₃ outer layers and Al₂O₃ inner layer.