Fe-14Cr-Mn合金在不同温度熔融共晶NaCl-MgCl2中腐蚀行为及机理研究

熔融共晶NaCl-MgCl₂作为太阳能中高温相变储热介质,运行状态下其温度常在熔点附近波动。但不同温度下该熔融盐对金属容器材料腐蚀行为不清楚。以Fe-14Cr-Mn合金为例,采用浸盐法研究了718K、768K和818K熔融共晶NaCl-MgCl₂对该合金的腐蚀行为,探讨了腐蚀机理。结果表明：腐蚀速率随温度增加略微增加,三种温度下试样腐蚀动力学曲线服从线性规律(斜率约k=-4.806E-4)。腐蚀初期,试样表面形成泡状腐蚀产物,腐蚀80h后形成腐蚀坑洞,主要是Fe、Fe-Cr和MgO,也检测到含微量Fe和Ni的Mg-Fe-Ni的氧化物。腐蚀机理主要是MgCl₂吸潮后以H₂O形式引入的氧原子和溶解在熔融盐中的微量氧作为阴极去极化剂,合金元素Cr和Mn与Cl_-反应生成的氯化物,氯化物吸附水分子,形成具有低熔点的含水氯化物(如CrCl₃.6 (H₂O) 和MnCl₂.n (H₂O))逃逸腐蚀体系。另外,在熔岩表面形成了由MgCl₂. (H₂O) ₆, NaCl 和 MgO组成的盐壳,而在熔融盐内部,NaCl与NaMgCl₃共存。本研究为研发耐熔融NaCl-MgCl₂腐蚀的新合金奠定了基础。     

碳钢和铁-铬-镍基合金在相变储能材料用熔融共晶氯化钠和氯化镁中的腐蚀行为

研究了3种铁-铬-镍基合金(Fe-Cr-Ni)和一种碳钢试样在520℃熔融共晶NaCl-MgCl2盐中的腐蚀行为。结果表明,碳钢试样晶界处Fe原子优先变为亚铁离子(Fe2+)和铁离子(Fe3+),发生了严重的沿晶腐蚀,但表面形成了厚而致密的MgO壳,对试样起到了一定的保护作用。3种Fe-Cr-Ni基试样表面也形成了MgO壳,但因铬元素优先被腐蚀,试样表面形成了疏松的富Ni骨架状微观组织结构,MgO壳或颗粒极易剥落,未能起到有效的保护作用;Cr含量越高,腐蚀越严重。对于太阳能储能技术,在廉价的铁基合金中添加镍元素作为熔融氯化盐相变储热介质的容器或者管道材料,具有良好发展前景。     

碳钢和铁-铬-镍基合金在相变储能材料用熔融共晶氯化钠和氯化镁中的腐蚀行为（英文）

研究了3种铁-铬-镍基合金(Fe-Cr-Ni)和一种碳钢试样在520℃熔融共晶NaCl-MgCl_2盐中的腐蚀行为。结果表明,碳钢试样晶界处Fe原子优先变为亚铁离子(Fe~(2+))和铁离子(Fe~(3+)),发生了严重的沿晶腐蚀,但表面形成了厚而致密的MgO壳,对试样起到了一定的保护作用。3种Fe-Cr-Ni基试样表面也形成了MgO壳,但因铬元素优先被腐蚀,试样表面形成了疏松的富Ni骨架状微观组织结构,MgO壳或颗粒极易剥落,未能起到有效的保护作用;Cr含量越高,腐蚀越严重。对于太阳能储能技术,在廉价的铁基合金中添加镍元素作为熔融氯化盐相变储热介质的容器或者管道材料,具有良好发展前景。     

基于磁过滤技术的热障涂层表面Al2O3 覆盖层抗CMAS腐蚀性能

为了提高热障涂层（TBC）的抗沉积物（主要成分为CaO、MgO、Al₂O₃和SiO₂,简称CMAS）腐蚀性能,采用磁过滤阴极真空电弧（FCVA）技术在TBC表面上制备了致密的Al₂O₃覆盖层,比较和分析了Al₂O₃改性TBC和沉积态TBC的润湿行为和抗CMAS腐蚀性能。结果表明：使用FCVA技术制备Al₂O₃覆盖层的过程对7%（质量分数）氧化钇稳定的氧化锆（7YSZ）相的结构无明显影响,且经Al₂O₃改性的TBC综合性能均优于沉积态TBC。在1250 ℃、CMAS腐蚀条件下,Al₂O₃覆盖层有效地限制了熔融CMAS在TBC表面上的扩散行为。同时,Al₂O₃填充了7YSZ柱状晶之间的间隔并且阻碍了熔融CMAS的渗透,证明了FCVA可作为一种制备Al₂O₃涂层的新方法以提高TBC的抗CMAS腐蚀性能,且Al₂O₃涂层及其制备过程对TBC的热震性能均无消极影响。     

Li4SiO4 氚增殖陶瓷的制备及其与14Cr-ODS钢的腐蚀界面行为

Li₄SiO₄小球与ODS钢的化学相容性对聚变反应器的安全运行具有重要意义。研究了在500、600、700 ℃的氩气环境中保温300 h后ODS钢与小球接触界面组织和成分的变化。结果表明,在600~700 ℃时,Li₄SiO₄小球与ODS钢的界面发生了严重的元素互扩散和反应。在Li₄SiO₄小球表面,由于ODS钢中Fe和Cr的扩散,出现了一层薄薄的反应层,这也导致了密度的增加,破碎负荷从51 N （500 ℃）下降到32 N（700 ℃）。XRD图谱显示,ODS钢表面出现了LiCrO₂和LiFeO₂新相,说明Li₄SiO₄小球中的Li和O原子可以扩散到ODS中,与Fe、Cr元素在高温下发生反应形成腐蚀层。在700 ℃时,腐蚀层可分为2个氧化层。最外层是LiFeO₂和LiCrO₂的混合物,下一层主要是LiFeO₂。在ODS钢的表面,700 ℃/300 h条件下氧扩散系数为2.2×10^-14 cm²/s,这说明ODS钢作为一种包层结构材料,在未来的包层设计中需要一层耐腐蚀涂层。     

酸刻蚀处理对IrO2-Ta2O5/Ti阳极寿命的影响

通过改变腐蚀方法,研究了使用H₂C₂O₄和H₂SO₄进行钛基体表面刻蚀对金属氧化物钛阳极电化学性能和表面形貌的影响。采用扫描电子显微镜、X射线衍射仪和光电子能谱等测试方法对样品进行了结构分析。然后利用电化学工作站测试了样品的电催化活性,利用加速寿命测试研究了样品的电化学稳定性。结果表明,通过H₂C₂O₄和H₂SO₄分步腐蚀可以获得更加均匀致密的表面形貌和更好的催化稳定性。在此基础上,进一步研究了预处理对钛阳极寿命的影响原因。IrO₂-Ta₂O₅/Ti阳极的催化活性和稳定性与酸刻蚀处理的先后顺序及表面结构密切相关,并建立了预处理方法与阳极性能之间的关系。分步腐蚀使钛表面具有合适的粗糙度,因而提升了涂层附着力。在热分解过程中,经分步腐蚀形成的氢化钛在不改变表面形貌的情况下转变为金红石结构的氧化钛,有利于电子输运,从而增强涂层附着力并延长加速寿命。     

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。     

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。     

原子层沉积Al2O3 保护层氢终端金刚石MISFETs的电学特性

研究了Zr-Si-N氢终端金刚石（H-diamond）绝缘栅场效应晶体管（MISFET）在有无Al₂O₃保护层情况下的电学特性。分别采用原子层沉积法（ALD）和射频溅射法（RF）制备了Al₂O₃保护层和Zr-Si-N栅介质层。MISFETs的转移特性曲线表明,其栅阈值电压在有无Al₂O₃保护的情况下从-2.5 V变化到3 V,表明器件从常关型转换为常开型。输出和转移特性曲线揭示了氧化铝的存在保护了氢终端,使其免受磁控溅射过程的损伤。     

NH4HF2 氟化Al2O3 制备无水AlF3 研究

采用热重-差热分析（TG-DTA）方法对不同NH₄HF₂/Al₂O₃质量比的Al₂O₃+NH₄HF₂混合物的热行为进行了分析,确定了DTA曲线的临界温度。进一步分析了各临界温度前后直接热处理所得产物的形貌和物相。结果表明,质量比对临界反应温度和反应过程没有影响。氟化反应在室温下以(NH₄)₃AlF₆的形成开始,在162.3~162.8 ℃时占主导地位,在180 ℃左右完成。进一步热处理后,(NH₄)₃AlF₆在249.8~250.1 ℃分解为NH₄AlF₄,在356.8~357.7 ℃分解为β-AlF₃;随后β-AlF₃在400~650 ℃向α-AlF₃转变。     

Hot Corrosion Behavior of Inconel 625 Superalloy in Eutectic Molten Nitrate Salts

Corrosion resistance of Inconel 625 Ni-based superalloy was studied in a molten nitrate salt consisting of 40 KNO₃–60 NaNO₃ (wt%) at 500 and 600 °C. Open-circuit potential, potentiodynamic polarization, electrochemical impedance spectroscopy and gravimetric tests were used to evaluate the degradation mechanism and corrosion behavior of the alloy. Surface morphology and chemical analysis of corrosion products were characterized by means of scanning electron microscopy and energy-dispersive X-ray spectrometry. The weight-loss curves showed that with the increase in temperature, the oxidation rate and mass gain increased; the relationship between the mass gain and time was close to the parabolic oxidation law. The electrochemical corrosion results confirmed that during the exposure of Inconel 625 alloy to the molten salts, nickel dissolves as a result of non-protective NiO layer formed. The formation of a non-protective oxide layer with low barrier property was responsible for observing the weak corrosion resistance of the alloy at high temperatures (500 and 600 °C). Cyclic polarization tests showed a positive hysteresis confirming the nucleation and growth of stable pits on the surface of Inconel 625 at high anodic overpotentials. Sodium nitrite acts as an efficient pitting inhibitor for this case. In this way, the sodium nitrite with the concentration of 0.1 molal was found to have an optimum inhibition effect on pit nucleation at 600 °C.     

Inconel625合金及焊缝在Na2SO4-NaCl熔盐中热腐蚀行为研究

对Inconel625母材与焊缝金属进行750℃下的75%Na₂SO₄-25%NaCl混合熔盐热腐蚀实验，并对腐蚀产物的物相、表面形貌、腐蚀失重速率及腐蚀机理等进行分析。结果表明：Inconel625接头母材处组织为奥氏体等轴晶，焊缝处组织为树枝晶；母材与焊缝金属失重曲线均遵循抛物线规律，其失重速率常数分别为3.43和4.18 mg²·cm^-4·h^-1；焊缝金属因为富Nb第二相的析出，导致其与母材相比耐蚀性较差，腐蚀表现出“不均匀性”；2种状态下的Inconel625有着相同的腐蚀层结构均为：外层NiO颗粒和片层状NiCr₂O₄，中层致密Cr₂O₃氧化层，内层“蜂窝”状Ni₂S₃硫化层的3层结构。Inconel625合金在750℃下75%Na₂SO₄-25%NaCl混合盐中的主要腐蚀机理为“硫化-氧化”腐...     

High-Temperature Corrosion Studies of HVOF-Sprayed Cr3C2-NiCr Coating on SAE-347H Boiler Steel

Cr₃C₂-NiCr coating was deposited on SAE-347H boiler steel by high velocity oxy fuel (HVOF) spray process. Subsequently, high-temperature corrosion behavior of the bare and coated boiler steel was investigated at 700 °C for 50 cycles in Na₂SO₄-82Fe₂(SO₄)₃ molten salt, as well as air environments. Weight-change measurements after each cycle were made to establish the kinetics of corrosion. X-ray diffraction, field emission-scanning electron microscopy/energy dispersive spectroscopy, and x-ray mapping analyses were performed on the exposed samples to analyze the oxidation products. The bare 347H steel suffered accelerated oxidation during exposure at 700 °C in the air as well as the molten salt environment in comparison with its respective coated counterparts. The HVOF-spray Cr₃C₂-NiCr coating was found to be successful in maintaining its adherence in both the environments. The surface oxide scales were also found to be intact. The formation of chromium rich oxide scale might have contributed for the better hot corrosion/oxidation resistance in the coated steel.     

Hot Corrosion Mechanism of Steels Exposed to Heavy Metal Chlorides and Sulphates in SO<Subscript>2</Subscript> Environment

Copper flash smelting produces flue dust containing SO₂-rich exhaust gas, causing corrosion problems in the heat recovery boiler of the gas train. In order to understand the corrosion behaviour of boiler steels, conditions of the boiler were simulated in the laboratory. Corrosion damage occurred as chlorine reacted with steel surfaces forming chlorides which deplete the steels from their alloying metals. At the scale/dust deposit interface, where the highest sulphur partial pressures prevail, a sulphate layer covered the mixed oxide and chloride scale. Molten sulphate deposit reduced the metal loss of AISI 304 steel by preventing chromium chloride diffusion away from the steel surface. The Cr₂O₃ scales were quite stable under molten sulphates. The dust deposit melted partially due to the presence of ZnCl₂ in the deposit which initiated corrosion damage by producing a molten salt layer on the steel surfaces bringing it in contact with aggressive compounds in the copper smelter flue dust.     

铸铁材料在盐湖卤水中的腐蚀研究

在青海盐湖卤水中试验了四种钢铁材料的腐蚀,测定了灰口铸铁表面形成的覆盖物和腐蚀产物的形貌、组成.分析了盐湖卤水及腐蚀产物对铸铁腐蚀性的影响.铸铁在盐湖卤水中表现出典型的"石墨化"腐蚀,形成的网状石墨骨架层有利于减少铸铁的腐蚀.极高的CL离子浓度未造成铸铁点蚀.     

纳米 NiCrBSi-TiB2 涂层在硫酸熔盐中的热腐蚀行为研究

目的研究纳米NiCrBSi-TiB2涂层在800℃下的Na2SO4-30%(质量分数)K2SO4熔盐中的热腐蚀行为。方法采用超音速火焰技术在中碳钢表面喷涂纳米NiCrBSi-TiB2涂层,以饱和Na2SO4-30%K2SO4溶液为腐蚀介质,研究该涂层在800℃时的热腐蚀行为。结果微米涂层晶粒粗大,Si的扩散系数低,易出现贫Si富Cr层,形成的Cr2O3膜在碱性熔盐中具有较低的溶解度,对涂层具有良好的保护作用。结论微米涂层在Na2SO4-30%K2SO4熔盐中具有更优的抗热腐蚀性能。     

High Temperature Corrosion of the Alloy Ni4Mo in a hydrogen chloride atmosphere

Specimens of the alloy Ni₄Mo were tested in a hydrogen chloride atmosphere at temperatures between 400° – 850° C. The corrosion of the alloy was followed by gravimetric analyses and microstructural examinations. It was found that the layer formed on the specimens due to corrosion is adherent but porous, thus allowing the volatilization of some of the corrosion products. The formation of various kinds of oxides and chlorides was observed. The exact composition of the scale depended on the temperature of exposure to hydrogen chloride and on the amount of oxygen present as an impurity in the test apparatus. The formation of a domain structure in the uncorroded alloy affects the morphology of the scale/alloy interface.     

Corrosion of carbon steel underneath a lead/potassium chloride salt mixture

High amounts of lead in waste/recycled wood fuel are known to be a contributing factor to the increased corrosion often related to this type of fuel. In combination with potassium, usually present in the fuel, low‐melting point salt mixtures between lead chloride (PbCl ₂) and potassium chloride (KCl) are expected to form. The purpose of this study is to investigate reactions in the mixed salt of PbCl ₂ and KCl and its interactions with carbon steel P265GH and its oxide. Laboratory exposures were performed in an isothermal tube furnace with a salt mixture of PbCl ₂/KCl (50/50 mol%) put on steel samples. The test duration was 24 hr at either 300°C or 340°C in an atmosphere of 100 ppm HCl and 20 vol% H ₂O in synthetic air. After exposure, the salt mixture consists of distinct areas of KCl and PbCl ₂ but also the compounds K ₂PbCl ₄ and KPb ₂Cl ₅. A general observation is that the oxide thickness increases with temperature and that areas with Pb/K‐mixed salt are frequently found in close connection to more corroded areas. Often the more lead‐rich phase KPb ₂Cl ₅ is located closest to the corrosion product indicating its importance for the corrosion.