TBCs粘结层抗高温氧化行为研究

该文采用超音速火焰喷涂方法,在镍基高温合金基体上制备NiCoCrAlTaY粘结层,通过XRD、SEMi析方法,研究了相同温度不同氧化时间粘结层的抗高温氧化行为及氧化机理,分析计算得到粘结层的氧化动力学规律,最后总结了控制TGO生长的方法。分析表明：TGO的生长使粘结层Al元素贫化,Ni、Cr元素氧化产生复杂的尖晶石类金属氧化物,是粘结层抗氧化性能降低的根本原因,为热障涂层的结构设计及优化提供了依据。     

DD5单晶叶片用热障涂层高温防护性能研究

为了提高燃气轮机热端部件的服役寿命,拓展热端部件的高温防护方法及应用,在某燃气轮机涡轮叶片用DD5镍基单晶高温合金表面制备了CoCrAlY+YSZ,(Ni, Pt)Al+YSZ和Zr改性(Ni, Pt)Al+YSZ 3种热障涂层,对比研究了这3种热障涂层的1 100℃循环氧化行为和900℃混合盐热腐蚀行为。结果表明：CoCrAlY+YSZ涂层在循环氧化和热腐蚀过程中均发生严重的YSZ陶瓷面层剥落现象,而铝化物+YSZ涂层的陶瓷面层则完好或仅局部极少量剥落;(Ni, Pt)Al涂层经活性元素Zr改性后抗氧化和耐热腐蚀性能均进一步提高,表现为氧化和腐蚀增重降低,内氧化和内硫化现象明显减轻;(Ni, Pt)Al+YSZ涂层和Zr改性(Ni, Pt)Al+YSZ涂层对DD5镍基单晶高温合金叶片均有较好的适用性。     

Al基涂层和Ni-Cr基涂层抗蒸汽氧化性能研究

对T91+Al基涂层和T91+Ni-Cr基涂层在600℃/27 MPa蒸汽参数下的氧化性能进行了研究,氧化1 300 h后,利用扫描电子显微镜(SEM)和能谱仪(EDS)分析了氧化膜表面及横截面形貌、微观组织结构和元素分布。结果表明:Al基涂层和Ni-Cr基涂层的抗蒸汽氧化性能显著优于T91钢试样,且Al基涂层的抗蒸汽氧化性能优于Ni-Cr基涂层;蒸汽氧化过程中Al基涂层表面形成了以Al的氧化物(Al氧化物为主,一定量的Si氧化物和Cr氧化物)为主的连续致密氧化膜;蒸汽氧化过程中Ni-Cr基涂层表面形成了富Ni和Cr的氧化膜。     

Inconel 740合金在空气和含有水蒸气的空气中的氧化研究

利用热重分析法、X射线衍射仪和扫描电镜与能谱分析仪研究了Inconel 740合金在空气和含有水蒸气的空气中的高温氧化行为,并分析了该合金的氧化机制.结果表明：Inconel 740合金在950℃的静态空气中氧化时,氧化动力学遵循抛物线规律,氧化膜黏附性能良好,表面氧化膜完整,外层由Cr2O3和少量的（Ni,Co）Cr2O4、TiO2组成,中间层为SiO2和Al2O3,内层氧化物为Al2O3和TiO2;合金在750℃含有10%水蒸气的空气中的腐蚀动力学也近似遵从抛物线规律,表面氧化膜很薄且致密性较差,表面氧化层主要为Cr2O3,内层氧化物为Al2O3和TiO2.     

低温渗铝涂层对P92钢650℃饱和蒸汽氧化行为的影响

利用低温粉末包埋渗法在P92钢服役温度下制备了铝化物涂层,并结合氧化增重法、扫描电镜观察及X射线衍射分析,研究了P92钢及其铝化物涂层在650℃下的饱和蒸汽氧化行为。结果表明:P92钢抗蒸汽氧化性能不足,350 h前氧化动力学遵循抛物线规律,外层疏松层氧化物Fe_3O_4+Fe_2O_3与内层氧化物FeCr_2O_4呈双层结构,氧化700 h后外层氧化膜发生严重剥落;低温包埋渗铝后,试样表面形成保护性Al_2O_3氧化膜,可显著提升P92钢抗蒸汽氧化性能;Al_2O_3氧化膜具有较慢的生长速度,因此铝化物涂层的耗损并不是继续形成Al_2O_3带来的消耗,而是Al向内扩散形成AlN相以及Fe向铝化物涂层扩散形成Fe_3Al相,从而降低Al浓度梯度。     

铝硅合金活塞表面无色化学氧化技术

本文介绍了本公司提高铝硅合金活塞耐蚀性能的无色化学氧化工艺及其主要工序的溶液配方、工艺条件、操作要求；试验分析了无色化学氧化溶液各因素对氧化膜耐蚀性的影响和氧化膜的抗蚀性能；采用此工艺既提高了铝硅合金活塞耐蚀性，又保持了铝基光泽，工艺简单，效率高，适宜批量生产。     

超超临界汽轮机用低膨胀高温合金

介绍了超超临界汽轮机用低膨胀高温合金的国内外研究情况。通过分析合金元素、γ′相含量、γ′相中Al/Ti比等因素对合金热膨胀系数、高温性能以及锻造等工艺性能的影响,介绍了国内外超超临界汽轮机用低膨胀高温合金的各项性能,比如合金组织、物理性能、拉伸性能、蠕变持久性能、抗氧化腐蚀性能、长时组织稳定等等,为我国高参数汽轮机用低膨胀高温合金材料的研发提出了建议。     

1Cr11MoNiW1VNbN不锈钢硼砂盐浴渗铬性能研究

文章通过硼砂熔盐对1Cr11MoNiW1VNbN不锈钢进行盐浴渗铬处理,利用光学显微镜(OM)、扫描电镜(SEM)、X射线衍射(XRD)和显微硬度计对1Cr11MoNiW1VNbN不锈钢盐浴渗铬后渗层的深度、组织结构以及硬度进行分析,利用摩擦磨损试验、高温长时氧化试验和电化学等方法测试渗铬层的摩擦性能、高温抗氧化性能以及耐蚀性能。结果表明,1Cr11MoNiW1VNbN不锈钢经硼砂盐浴1 035℃×3 h渗铬处理后,获得最外层白亮层Cr_(23)C_6,约3μm,局部次外层产生Fe-Cr固溶体,局部渗层总厚度达10μm。白亮层硬度达1 690 HV。结果还表明渗层的存在提高了材料的摩擦磨损性能、高温抗氧化性能以及耐蚀性能,可提高1Cr11MoNiW1VNbN材料螺栓抗咬死性能。     

超临界机组的合金管蒸汽侧氧化膜生长与剥落研究进展

超临界机组高温合金管氧化膜剥落问题是困扰机组安全与经济运行的难题,严重制约了机组蒸汽参数和效率的提高。特别是,在超临界机组采用给水加氧处理方式(OT)后,奥氏体不锈钢管内壁氧化膜大面积剥落事故屡见不鲜,尤以TP347H合金管为甚。本文总结了近年来国内外针对超临界机组合金管氧化膜研究的进展及相关成果,首先介绍了超临界蒸汽环境中合金管氧化机理和原子迁移机制,综述了铁素体和奥氏体合金表面氧化膜的形貌特征,分析了蒸汽溶氧对氧化膜生长速率、形貌和缺陷的影响。氧化膜完整性是决定合金抗腐蚀性能的重要因素,但在机组运行过程中氧化膜应力破坏了氧化膜完整性。进一步总结了国内外氧化膜应力和剥落研究的数值分析及实验研究情况,为我国超临界机组氧化膜剥落故障诊断研究提供参考。     

HR3C在750℃空气和水蒸气中的高温氧化行为研究

利用扫描电子显微镜、X射线衍射仪等对奥氏体不锈钢HR3C在750℃静态空气和纯水蒸气中的高温氧化行为进行了对比研究,基于对氧化膜微观结构的细致表征,探讨了HR3C在2种气氛中的氧化机制.结果表明:在2种气氛中,HR3C表面均形成连续的(Cr,Mn)2O3膜;静态空气中HR3C合金的氧化动力学均呈现分段式抛物线规律;水蒸气的存在使得(Cr,Mn)2O3膜破裂这一过程提前并大幅加速合金的氧化,导致纯水蒸气中HR3C的氧化动力学整体偏离抛物线规律;(Cr,Mn)2O3膜的破裂是膜与基体界面空洞和膜内生长应力综合作用的结果,这使得裸露的金属基体直接与高温空气或水蒸气反应,形成Fe3O4瘤状物.     

Improved oxidation resistance of a nanocrystalline chromite-coated ferritic stainless steel

An economical dip coating process was developed to synthesize uniform, crack-free, and adherent thin nanocrystalline LaCrO₃ films on a ferritic stainless steel substrate for the solid oxide fuel cell interconnect applications. LaCrO₃ perovskite phase was formed after annealing in air at 800 °C for 1 h for both the LaCrO₃ and La₂O₃ precursors. The effectiveness of the coating in improving the oxidation resistance of the alloy was demonstrated by both isothermal and cyclic oxidation tests. The LaCrO₃ coatings were found to cause a pronounced reduction in oxidation rate of the alloy, especially with low La-content precursors. The area-specific resistance of the oxide scales formed on the bare and coated alloy substrates was also evaluated and discussed.     

Development of high strength ferritic steel for interconnect application in SOFCs

High-Cr ferritic model steels containing various additions of the refractory elements Nb and/or W were studied with respect to oxidation behaviour (hot) tensile properties, creep behaviour and high-temperature electrical conductivity of the surface oxide scales. Whereas W additions of around 2 wt.% had hardly any effect on the oxidation rates at 800 and 900 °C, Nb additions of 1% led to a substantially enhanced growth rate of the protective surface oxide scale. It was found that this adverse effect can be alleviated by suitable Si additions. This is related to the incorporation of Si and Nb into Laves phase precipitates which also contribute to increased creep and hot tensile strength. The dispersion of Laves phase precipitates was greatly refined by combined additions of Nb and W. The high-temperature electrical conductivity of the surface oxide scales was similar to that of the Nb/W-free alloys. Thus the combined additions of Nb, W and Si resulted in an alloy with oxidation resistance, ASR contribution and thermal expansion comparable to the commercial alloy Crofer 22 APU, but with creep strength far greater than that of Crofer 22 APU.     

钼黑太阳能选择性吸收涂层的研制

利用NH_4Cl、(NH_4)_6Mo_7O_(24)·4H_2O的水溶液为原料液在经过预处理后的铝或铝合金基片上进行化学沉积,制备钼黑太阳光谱选择性涂层。实验考察了反应时间、反应温度、反应溶液的pH值和表面预处理方式等对涂层太阳吸收率α的影响,得到了制备钼黑涂层的优化条件,并对涂层表面进行了XPS及SEM表征。实验结果表明,涂层由Mo_xO_y组成,Mo的化学态介于 4～ 6之间;铝基片制得的涂层的吸收率明显高于铝合金基片;反应温度和反应时间对于涂层的吸收率影响较为明显;基片经碱性预处理后涂层的太阳吸收率优于酸性预处理。     

LaCrO3-based coatings deposited by high-energy micro-arc alloying process on a ferritic stainless steel interconnect material

Currently used ferritic stainless steel interconnects are unsuitable for practical applications in solid oxide fuel cells operated at intermediate temperatures due to chromium volatility, poisoning of the cathode material, rapidly decreasing electrical conductivity and a low oxidation resistance. To overcome these problems, a novel, simple and cost-effective high-energy micro-arc alloying (HEMAA) process is proposed to prepare LaCrO₃-based coatings for the type 430 stainless steel interconnects. However, it is much difficult to deposit an oxide coating by HEMAA than a metallic coating due to the high brittleness of oxide electrodes for deposition. Therefore, a Cr-alloying layer is firstly obtained on the alloy surface by HEMAA using a Cr electrode rod, followed by a LaCrO₃-based coating using an electrode rod of LaCrO₃-20 wt.%Ni, with a metallurgical bonding between the coating and the substrate. The preliminary oxidation tests at 850 °C in air indicate that the LaCrO₃-based coatings showed a three-layered microstructure with a NiFe₂O₄ outer layer, a thick LaCrO₃ sub-layer and a thin Cr₂O₃-rich inner layer, which thereby possesses an excellent protectiveness to the substrate alloy and a low electrical contact resistance.     

High-temperature oxidation process analysis of MnCo2O4 coating on Fe-21Cr alloy

Even though the operation temperature of solid oxide fuel cells (SOFCs) stacks has been reduced (∼750 °C), stainless steel interconnect within the stacks still requires protection by high conductive coatings to delay the growth of oxide scales and reduce chromium evaporation. Manganese cobaltite spinel protective coating with a nominal composition of MnCo₂O₄ was produced on Fe-21Cr stainless steel. Electrical, microstructural and compositional analysis were performed to investigate the interfacial reaction of MnCo₂O₄ protective coating with the stainless steel substrate during 750 °C oxidation process. The spinel coating not only acts as a barrier to Cr outward transport, but also improves the electrical conductivity of the alloy interconnect during long-term oxidation. The coated alloy demonstrates good electrical conductivity with an area specific resistance (ASR) of about 5 mOhm cm² after oxidation for 1000 h at 750 °C, which is about 1/4 of the ASR of bare Fe-21Cr alloy. The reduction of ASR might be caused by the fact that Cr migrated from the steel substrate interact with MnCo₂O₄ coating and generated Mn-Co-Cr spinel phase, which has higher electrical conductivity than that of Cr₂O₃.     

Titanium–tin oxide protective films on a black cobalt photothermal absorber

We report the effect of covering an electrodeposited black cobalt absorber film with a Ti : Sn oxide film at various atomic ratios prepared by the sol–gel dip process. The resulting composite was characterized in its optical, structural and morphological properties. After thermal treatment at 400°C, the uncoated black cobalt film is oxidized and Co₃O₄ is formed. Samples covered with Ti : Sn films and thermally treated at the same temperature suffered lower oxidation maintaining in great extent the original metallic cobalt structure. The optical properties of the resulting material were affected by the presence of the Ti : Sn coating, and the best protective film obtained was a transparent Ti : Sn (8 : 2) atomic ratio oxide film, with a 210 nm thickness. This composite system exhibits an absorptance value of 0.91 and an emittance value of 0.34 after a 100 h, 400°C thermal treatment. A photothermal material composed of a layer of black cobalt and a protective oxide film coating seems then a promising solar energy absorber capable of withstanding high operating temperatures (400°C).     

Efficient synthesis of Pt3Co/NC alloy catalysts with enhanced durability and activity for the oxygen reduction reaction

Lack of catalytic performance, short life, and high cost are three main problems related to JM-Pt/C catalysts for proton exchange membrane fuel cells. The introduction of cheap transition metals improves catalytic performance while significantly reducing the cost of the catalysts. Here, we report the synthesis of Pt₃Co/NC alloy catalysts via coating and pyrolysis treatment. The agglomeration of nanoparticles during the high-temperature alloying process is significantly inhibited by coating with PANI. Remarkably, the obtained Pt₃Co/NC alloy catalysts exhibit excellent ORR catalytic performance and structural stability in 0.1 mol/L HClO₄. After 30,000 potential cycles, the mass activity and area-specific activity of Pt₃Co/NC alloy catalysts are 1.949 and 3.936 times higher, respectively, than that of JM-Pt/C with negligible performance loss. The strong metal-support interaction between N and Pt and the Pt-rich surface restrict the dissolution of Pt and Co, resulting in excellent stability. This synthesis approach provides an effective way to develop active and stable Pt alloy catalysts.     

Effect of Mn-Co spinel coating for Fe-Cr ferritic alloys ZMG232L and 232J3 for solid oxide fuel cell interconnects on oxidation behavior and Cr-evaporation

Metallic materials, especially Fe-Cr ferritic alloys, are promising as interconnect materials of solid oxide fuel cells (SOFCs) operated at around medium temperatures. ZMG232L is one of the developed Fe-Cr ferritic alloys for SOFC metallic interconnects.These metallic materials are usually machined or pressed into various shapes of interconnect parts, and thickness of these parts is often thin. However, the oxidation rate of thin sheet was much higher than that of thick one because Cr content decreased under oxide layer of edge part of thin sheet. Such accelerated oxidation behavior could be improved by reducing Mn, increasing Cr, and adding W in ZMG232L.It is also very important to reduce Cr-evaporation from the oxidized surface of ferritic alloys in cathode side. The aim of this study is to reduce the Cr-evaporation from oxidized alloy surface in air by coating with Mn-Co spinel oxide. In this study, oxidation behavior and Cr-evaporation of ZMG232L and improved Fe-Cr alloy, 232J3, coated with Mn-Co spinel oxide were investigated at elevated temperature in air. MnCo₂O₄ spinel coating on the pre-oxidized Fe-Cr ferritic alloy surface improved oxidation resistance and Cr-evaporation.     

Modification of the La0.6Sr0.4CoO3 coating deposited on ferritic stainless steel by spray pyrolysis after oxidation in air at high temperature

The behaviour of La_0.6Sr_0.4CoO₃ applied to ferritic stainless steel (AISI 430) by spray pyrolysis was investigated after oxidation at 800 °C in air. The film was characterized with regard to its morphology, structure and adhesion. The film was regular over the entire surface and adhered well to the metallic substrate. Oxidation modified the film structure, forming an oxide (SrCrO₄) in the metal/coating region due to Sr diffusion from the coating and Cr diffusion from the metallic substrate. A thermodynamic computational simulation confirmed the formation and stability of this oxide.     

Preparation and hydrogen penetration performance of TiO2/TiCx composite coatings

Titanium carbide is a good candidate for tritium permeation barrier in a fusion reactor. However, its oxidation susceptibility and the mismatch between the ceramic coating and substrate are still a challenge. In this study, a promising candidate as a hydrogen permeation barrier, comprising a titanium-based ceramic TiO₂/TiC_x composite coating, was proposed. The preparation process of this TiO₂/TiC_x composite coating involves two steps of carbon ion implantation and oxidation under ultra-low oxygen partial pressure. According to the results, the optimal oxidation temperature for TiO₂ coating is 550 °C, with the increase of the oxidation temperature, the particles on the surface of the oxide layer become coarse and loosely arranged, and the protective performance of the oxide layer is greatly reduced. The hydrogen barrier permeation behavior of the composite coating in a fusion reactor was simulated via hydrogen plasma discharge environment, the results show that the hydrogen barrier permeation performance of the composite is significantly better than that of a single TiO₂ coating. In addition, the coatings treated with hydrogen plasma showed a certain self-repairing performance through the diffusion growth of the TiC_x layer. These findings illustrate a novel method for preparing composite coatings to restrain hydrogen permeation, providing insight into the development of hydrogen permeation barrier materials.