炮钢表面的抗高温氧化性能研究

为了研究炮钢表面抗高温氧化性能,针对某型火炮身管材料PCr Ni3Mo钢进行了500,600,700℃、10 h恒温氧化试验,考察了其氧化动力学性能,利用纳米压痕仪测试了炮钢在不同氧化温度下的硬度与弹性模量,采用激光共聚焦显微镜、扫描电子显微镜(SEM)和X射线衍射仪(XRD)测试分析了不同氧化温度下的表面形貌和物相组成。结果表明:炮钢在空气中500℃氧化10 h后表面形成Fe_3O_4和Fe_2O_32种氧化物,600,700℃氧化10 h后表面形成Fe O、Fe_3O_4和Fe_2O_33种氧化物,其中700℃时表面氧化膜出现大量分层和剥落。     

水蒸气温度对700℃先进超超临界锅炉候选合金GH2984氧化行为的影响

采用X射线衍射仪、扫描电子显微镜对比研究GH2984合金在750℃和850℃纯水蒸气中的氧化行为。结果表明:GH2984合金的氧化动力学遵循抛物线规律;温度升高,Cr挥发加速,外氧化和内氧化的速率急剧增加,氧化膜的组成结构发生明显的变化。750℃时,合金表面形成单层致密的(Cr,Mn)_2O_3膜;温度升至850℃,氧化膜中空洞的数量大幅增加,氧化膜转变为由薄的外层Fe_2TiO_5和厚的次外层(Cr,Mn)_2O_3及薄的内层(Nb,Mo)_2O_5组成的三层结构。Ti,Al优先于晶界处发生内氧化,分别形成TiO_2和Al_2O_3;两种内氧化产物的尺寸和数量均随温度升高而增加。     

Fe-1Cr-0.2Si钢的高温氧化行为

为了明确三元系Fe-1Cr-0.2Si钢的高温氧化行为,采用管式电阻炉开展了空气条件下Fe-1Cr-0.2Si钢在900℃、1 000℃和1 100℃下氧化30 min的实验。结果表明:900℃时氧化铁皮由两层组成,外层为Fe_3O_4层,内层为FeO、FeCr_2O_4和Fe_2SiO_4的混合层。在1 000℃和1 100℃时,氧化铁皮层最外层为Fe_2O_3层,中间层为Fe_3O_4层和内部独立的FeO层,内层为FeCr_2O_4和含Si氧化物的混合层。在三个氧化温度下,Fe-1Cr-0.2Si整体的氧化铁皮结构分为两层:外层Fe的氧化物是以阳离子向外扩散为主生成,内层Cr和Si的氧化物是以O离子向内扩散为主产生。FeO层的厚度随着温度的升高逐渐增大。Cr和Si元素富集层厚度比例随着温度的升高而减小,但Cr和Si在混合层中的富集程度有所增加。经高温氧化后没有发现Cr和Si的复合氧化物,但Cr和Si的富集区没有出现明显的分层。     

不同Cr含量的Fe-Cr合金高温高压水蒸气氧化行为

Fe-Cr合金钢广泛用于锅炉的受热面管,但目前研究多针对Cr在高温常压环境中的氧化行为,对高温高压下的研究较少。对Cr的质量分数分别为9%、12%、18%、25%的Fe-Cr合金试样在650℃、25 MPa的高压水蒸气环境中的氧化行为进行研究,并与Cr-9的常压水蒸气氧化进行对比,采用扫描电镜(SEM)观察形貌、能谱分析成分变化、X射线衍射仪(XRD)分析物相组成并称重绘制氧化动力学曲线,以此来探究不同Cr含量的Fe-Cr合金的氧化膜生长规律和压强对其氧化行为的影响。结果表明:随着Cr含量的提高,Fe-Cr合金的孕育期增长,抗氧化能力得到提高;Cr含量的增加对氧化行为有一定影响,氧化66.0 h,Cr-9与Cr-12氧化动力学符合抛物线规律,在氧化初期就出现内外氧化层分层,内层为尖晶石FeCr2O_4,外层为Fe_3O_4,而Cr-18、Cr-25则仍处于孕育期,动力学几乎处于稳定状态,这个阶段主要是元素的扩散准备,氧化物的出现只是附加产物;表面的氧化物并不能构成一层完整的氧化膜,外加压强能够增加Fe-Cr合金位错和空位浓度,从而提高氧化速率,并且压强影响了氧化膜的形貌,在压应力的作用下,氧化膜主要由粒状氧化物构成。     

12Cr2MoWVTiB钢高温再热器管氧化膜的特征

电厂的12Cr2MoWVTiB钢高温再热器管实际运行中易出现氧化失效,为了对其实施有效的监督,采用扫描电镜、电子探针和X射线衍射对高温高压水蒸气下运行5.0×10~4h形成的氧化膜形貌、结构、成分及物相进行了分析.结果表明:氧化膜蒸汽侧形貌呈丘状或蘑菇云状,氧化膜基体侧呈方解石状,氧化膜横断面呈石状;氧化膜结构明显分为3层,外层、中间层和内层氧化膜均由粗大的柱状晶构成,各柱状晶层间有大量孔洞,而内层氧化膜与基体结合处氧化膜晶粒为细小等轴晶;O元素含量从外层氧化膜到靠近基体处,存在正的浓度梯度分布,而Fe,Cr,Mo元素含量存在负的浓度梯度分布,Cr,Mo元素在紧靠基体的氧化膜侧产生富集,含量均高于钢基体中的含量;氧化膜物相为Fe_3O_4和FeCr_2O_4.     

SIMP钢和T91钢在800℃的高温氧化行为

研究了ADS嬗变系统候选结构材料新型低活化马氏体耐热钢SIMP钢和T91钢在800℃空气中的高温氧化行为。结果表明,SIMP钢和T91钢在空气中氧化500 h后在表面形成了不同结构的氧化膜:在SIMP钢表面形成了连续致密的Cr_2O_3层,在Cr_2O_3层分布一层颗粒状的铬锰尖晶石,在基体和氧化膜之间出现硅的富集;而在T91钢表面形成了外层为Fe_2O_3和内层为铁铬尖晶石的双层结构氧化膜。新型SIMP钢的高温氧化速率远比T91钢的低,表现出优异的抗高温氧化性能。SIMP钢中较高的铬和硅元素含量,是其抗高温氧化性能优于T91钢的主要原因。     

涂覆Na_2SO_4-25%NaCl盐膜的Super304H的热腐蚀行为

应用增重分析法研究涂有Na_2SO_4-25%NaCl盐膜的Super304H在650,750℃空气中的腐蚀动力学曲线,采用XRD,SEM(EDS)和EPMA对腐蚀产物、腐蚀截面形貌和元素分布进行分析。结果表明:涂覆Na_2SO_4-25%NaCl盐膜的合金在650,750℃的腐蚀动力学曲线均呈"抛物线"趋势;合金表面形成了含CuFe_2O_4的富Fe氧化物(外层)与富Cr_2O_3(内层)组成的双层氧化膜以及含有孔隙的贫Cr、富Ni的腐蚀影响区;提高腐蚀温度或延长腐蚀时间均可以导致氧化膜与基体分离甚至剥落,腐蚀影响区孔隙密度增大,裂纹向基体延伸。分析认为:腐蚀初期合金发生选择性氧化,形成多层氧化膜;复合盐的熔融破坏氧化膜的完整性,加速氧化、氯化以及硫化的交互作用,导致内硫化和内氧化。     

溅射Ni_3Al微晶涂层的抗氧化性能

研究了铸态 Ni_3Al 合金及其微晶溅射涂层在1000—1100℃下等温氧化性能及1000℃下的循环氧化性能。结果表明:铸态 Ni_3Al 合金在氧化过程中形成 Al_2O_3,NiO 和 NiAl_2O_4 的复杂氧化膜;微晶 Ni_3Al涂层在氧化过程中形成α—Al_2O_3和 NiAl_2O_4尖晶石,不含 NiO,这种氧化膜的保护作用比含 NiO 的氧化膜的保护作用好,使得其氧化增重比铸态合金小约1半。此外铸态 Ni_3Al 合金在氧化过程中沿粗大晶界发生严重的内氧化,且表面氧化膜较脆易发生剥落;微晶 Ni_3Al 涂层可以消除沿晶界的内氧化,氧化膜与基体粘附良好,未发现剥落现象。微晶化大大提高了 Ni_3Al 合金的抗氧化性能。     

一种新型Ni-Fe-Cr基合金在模拟锅炉烟气中的腐蚀行为研究

应用X射线衍射仪、扫描电子显微镜、能谱仪等分析方法研究一种新型Ni-Fe-Cr基高温合金在700℃/750℃煤灰/烟气中的腐蚀行为。结果表明:750℃的腐蚀速率明显高于700℃,其腐蚀层的厚度由700℃的3μm增加到20μm。腐蚀1 000h后,SEM观察到Ni-Fe-Cr高温合金在700℃下表面有少量"瘤状"凸起产物,XRD结合EDS表明其腐蚀产物由表向里依次是结构疏松的NiO、Fe_2O_3和Fe3O4,内层为相对致密的Cr_2O_3、Al_2O_3和TiO2,基体和腐蚀层界面靠近基体一侧是多孔的硫化物。提高腐蚀温度到750℃表面出现更多凸起,并且出现了破裂。Cr_2O_3保护性氧化膜局部开裂或者剥落而形成"瘤状"凸起产物。氧化膜生长过程中的内应力以及温度降低产生的热应力共同作用,导致氧化膜开裂甚至与基体剥离。温度升高同样加剧熔融盐破坏氧化膜从而加快腐蚀进程。     

NiAl-28Cr-5.94Mo-0.05Hf-0.01Ho定向共晶合金的高温氧化行为

在900-1150℃氧化的NiAl-28Cr-5.94Mo-0.05Hf-0.01Ho定向共晶合金,在其表面生成了连续的Al_2O_3氧化膜,具有良好的抗氧化性能。定向凝固工艺使合金的组织细化并提高了Cr(Mo)相中Al元素的含量,以及加入微量稀土元素Ho,都有利于生成Al_2O_3氧化膜。在NiAl-28Cr 5.94Mo-0.05Hf-0.01Ho定向共晶合金的氧化过程中表面氧化膜发生相变θ-Al_2O_3→α-Al_2O_3,导致其1000℃氧化质量增加出现反常。     

Hot corrosion behavior of powder metallurgy Rene95 nickel-based superalloy in molten NaCl–Na2SO4 salts

Hot corrosion behavior of powder metallurgy (PM) Rene95 Ni-based superalloy in molten 25%NaCl + 75%Na₂SO₄ salts at 650 °C, 700 °C and 750 °C are investigated by weight loss measurements, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Experimental results show that hot corrosion kinetics follow a square power law at 650 °C and linear power laws at 700 °C and 750 °C. The corrosion layers on the surface of PM Rene95 superalloy are detected to be mainly composed of Cr₂O₃, NiO, and Ni₃S₂ at each temperature. Besides, small amounts of NiCr₂O₄ at 700 °C and NaCl at 750 °C are observed respectively. Cross-sectional morphologies and corresponding elemental maps indicate that corrosion layers near scale/alloy interface are composed of oxides at 650 °C while duplex oxides and sulfides at 700 °C and 750 °C. According to these results, a cooperating mechanism of oxidation and sulfuration for hot corrosion of PM Rene95 Ni-based superalloy is confirmed.     

Microstructure and spectral selectivity of Mo-Al2O3 solar selective absorbing coatings after annealing

Mo, Al₂O₃ single layer, Mo-Al₂O₃ granular cermet layer, Mo/Al₂O₃ tandem and an optimized Mo-Al₂O₃ multilayer coating with a double cermet layer configuration were deposited on stainless steel substrates by magnetron sputtering technique. The samples were annealed in vacuum at different temperatures ranging from 350 °C to 1000 °C for 2-5 h to evaluate their thermal stability. The spectral absorbance and thermal emissivity for the multi-layer selective coatings in the region of 1.3-25 μm were 0.91-0.93 and 0.19-0.27, respectively, depending on heat treatment temperature. Increasing annealing temperature has more obvious influence on the rise of emissivity than the drop of spectral absorbance. The microstructure, surface morphology, composition distribution and diffusion for various films before and after high temperature aging were investigated employing scanning electronic microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Fe₂O₃, as a diffusion barrier between Mo layer and SS substrate, effectively holds back the presence of Mo₂C and Fe₂MoC complex phases. Al₂O₃ is a stable phase even at 1000 °C for 3 h. However, defects such as widened boundaries, cracks and holes, which could appear in Al₂O₃ layer when heated at higher temperature than 650 °C, will provide the paths of Mo diffusion. Two diffusion modes of Mo, including inner self-congregation of Mo inside the cermet layer and Mo infiltration through the Al₂O₃ layer in Mo/Al₂O₃ tandem at 800 °C for 5 h, were observed after annealing.     

Thermal oxidation of single crystal aluminum nitride — A high resolution transmission electron microscopy study

The impact of the oxidation time on the structures of thermal oxides formed on AlN was determined by high resolution transmission electron microscopy (HRTEM). Oxidation of AlN single crystals was performed for 2 to 6 h at 1000 °C. Oxidation for 2 h produced mostly amorphous oxide layers whereas oxidation for both 4 and 6 h produced partially crystalline oxide layers. The oxide layer thickness varied from 205 to 600 nm for oxidation times of 2 and 6 h respectively. The crystalline oxide was mostly single phase α-Al₂O₃ except at the surface where it was a mixture of γ-Al₂O₃ and α-Al₂O₃. Based on the different structures produced for different oxidation times, we speculate that the oxide formed changes with thickness: first an amorphous oxide, then γ-Al₂O₃, and finally α-Al₂O₃ as the oxide thickness increases. The AlN crystal was nearly defect- and oxygen-free for oxidation at 1000 °C. This could be due to the rapid diffusion of the nitrogen and aluminum interstitials at a high temperature leading to a point-defect equilibrium throughout the nitride. A faceted interface between Al₂O₃ and AlN could be attributed to the surface diffusion to minimize energy.     

Cordierite as catalyst support for nanocrystalline CuO/Fe2O3 system

CuO, Fe₂O₃ and CuO–Fe₂O₃ samples supported on cordierite (commercial grade) were prepared by wet impregnation method using finely powdered support material, copper and/or iron nitrates. The extent of loading was varied between 5 and 20 wt.% CuO, Fe₂O₃ or CuO–Fe₂O₃. The physicochemical, surface and catalytic properties of the various solids calcined at 350–700 °C were investigated using XRD, EDX, nitrogen adsorption at 77 K and CO-oxidation by O₂ at 220–280 °C.The results obtained revealed that the employed cordierite preheated at 350–700 °C was well-crystallized magnesium aluminum silicate (Mg₂Al₄Si₅O₁₈). Loading of 20 wt.% CuO or Fe₂O₃ on the cordierite surface calcined at 350 °C led to a partial dissolution of the added oxides in the support lattice forming solid solutions. The other portions remained as separate nanocrystalline CuO or Fe₂O₃ phases. The dissolved portions of the transition metal oxide increased upon increasing the calcination temperature from 350 to 500 °C. Loading of 20 wt.% CuO–Fe₂O₃ on the cordierite surface followed by calcination at 350 °C resulted in a solid–solid interaction between some of CuO and Fe₂O₃ yielding iron cuprate Fe₂CuO₄, which decomposed at ≥500 °C yielding copper and iron oxides. The portion of Fe₂O₃ dissolved in the cordierite lattice at 500 °C is twice that of CuO.The S_BET of cordierite increased several times by treating with small amounts of Fe₂O₃ or CuO. The increase was more pronounced by treating with Fe₂O₃. The catalytic activity of the cordierite increased progressively by increasing the amount of oxide(s) added. The mixed oxides system supported on cordierite and calcined at 350–700 °C showed catalytic activities much bigger than those measured for the individual supported systems. The synergistic effect manifested in case of solids calcined at 350 °C was attributed to the formation of surface iron cuprate. The significant increase in surface concentration of copper species on top surface layers of the solids treated with mixtures of copper and ferric oxides could be responsible for the synergistic effect for the mixed oxide catalysts calcined at 500 or 700 °C.     

Effect of silicon content in steel and oxidation temperature on scale growth and morphology

The effect of high silicon content in steel, 1.6 wt.%Si and 3.2 wt.%Si, and high oxidation temperatures (850–1200 °C) on scale growth rate and morphology were investigated. The steels were oxidized in a 15% humid air with short isothermal oxidation times (15 min). The scale growth rate of the non-alloyed steel follows a parabolic law with time; it is an iron diffusion controlled oxidation. The presence of silicon delays scale growth by forming a silica SiO₂ barrier layer at the scale/metal interface, this effect is more important for the steel containing 3.2 wt.%Si and induces a discontinuous scale. Silicon oxides are concentrated at the scale/metal interface; their morphology depends on the oxidation temperature. For temperatures lower than 950 °C, silica is formed. Between 950 °C and 1150 °C, fayalite (Fe₂SiO₄) grains appear in the wüstite matrix close to the scale/metal interface. For temperatures higher than 1177 °C, a fayalite–wüstite eutectic is formed; this molten phase favours iron diffusion leading to high scale growth. After cooling, a continuous fayalite layer with small wüstite grains is obtained at the scale/steel interface.     

Scaling and intergranular oxidation of an Fe/48 wt% Ni alloy in carbon dioxide at 700 to 1000°C

The oxidation of Nilo 48 has been studied using thermogravimetric, metallographic, and electron probe microanalysis techniques at 700 to 1000° C. After a short period of ill-defined oxidation, the parabolic law was obeyed throughout the exposure period, which varied from 1050 h at 713° C to 50 h at 1000° C. The activation energy for the oxidation reaction was 48±6 kcal/mole. Examination of the external scale indicated that this was single phase and, at 1000° C, its composition corresponded to Ni_xFe^3–xO₄, wherex 0.4. There were also intergranular oxidation and nickel enrichment of the alloy underlying the external scale. After oxidation for only 10 min at 1000° C, the nickel-enriched alloy zone contained 65 wt % Ni. The manganese concentration in the scale was similar to that in the alloy. The results are discussed and compared with those of other workers and it is concluded that the rate-controlling process is the diffusion of iron through the Ni_xFe_3–xO₄ lattice.     

Effect of oxidation temperature on physical properties of thermally grown oxide on GaN in N2O ambient

Physical characterizations of thermally grown oxide on n-type GaN in N₂O ambient have been performed. The present study carried out the test at different oxidation temperature (700–1000 °C) in order to investigate the effect of oxidation temperature on the thermal oxide. Fourier Transform infrared spectrometer, X-ray diffraction and X-ray photoelectron spectroscopy were employed to identify the oxide layer formed on top of the GaN. Based on the analysis, Ga₂O₃ and GaON compounds were found on the sample oxidized at 700–900 °C. However, at 1000 °C, non-stoichiometry Ga_xO_y and/or Ga_xO_yN_z compounds were formed. Apart from that, atomic force microscope results indicated that protrusions of grains appeared on the surface after thermal oxidation. The surface roughness of the oxide layer was also found to be increased with temperature. Besides, cross-sectional energy filtered transmission electron microscopy image revealed that the thickness of the oxide layer was increased with oxidation temperature. Remarkably, the activation energy calculated from the Arrhenius plot was found to be 1.65 eV (159.22 kJ mol⁻¹).     

The effect of micro-structure on the oxidation behavior of a Ni-based superalloy in water vapor plus oxygen

The oxidation behavior of a Ni-based superalloy with polycrystalline, single-crystalline (SC) and nanocrystalline (NC) structures was studied at 1000 °C in water vapor (20.12 vol.%) plus oxygen. The oxidation behavior of the SC alloy was similar to that of the cast alloy, while nanocrystallization increased the corrosion resistance. The oxides scale on the SC alloy and cast alloy consisted of external TiO₂, Cr₂O₃ and internal Al₂O₃, while only external Al₂O₃ scale formed on the NC coating in water vapor plus oxygen. Meanwhile, the morphologies of oxides scale on three samples are significantly different from one another. The effect of micro-structures on the oxidation behavior of this Ni-based superalloy is discussed.     

The hydrolysis product of ferric nitrate in sodium hydroxide

The hydrolysis product of ferric nitrate is obtained by adding ferric nitrate solution to a boiling solution of 2.5 N sodium hydroxide. The sample is amorphous to X-rays when heated below 600° C, but it shows X-ray lines of -Fe₂O₃ at 650° C. Thermal analysis of the sample gives an endothermic peak at 80° C and two small exothermic peaks at 280° C and 700° C. Transmission electron microscopy and infrared spectroscopy confirm the primary particles as a defect form of FeOOH · H₂O. The defect FeOOH form of the sample converts to the disordered form of Fe₂O₃ on further heating around 700° C. The drastic fall in the surface area of the sample beyond 600° C suggests sudden growth of particle size, which is confirmed by a small endothermic peak at 700° C.     

Oxidation behaviour and strength of B4C-30 wt% SiC composite materials

The oxidation behaviour and the effect of oxidation on the room-temperature flexural strength of B₄C-30 wt% SiC composite material were investigated. The weight changes of the samples exposed to air at temperatures between 500 and 1000 °C were continuously monitored with a microbalance. At temperatures below 800 °C, the weight change of the specimen was negligible. As the temperature was increased to 800 °C, parabolic weight gain was observed. The rate of the weight gain increased with exposure temperature. The oxidation product formed on the surface was found to be a crystalline boric oxide (B₂O₃) by X-ray analyses. The oxide layer was severely cracked due to the thermal expansion mismatch between the oxide layer and the substrate. However, the room-temperature flexural strength was increased when the samples were exposed at temperature between 700 and 900 °C, apparently due to the blunting of strength-limiting defects at the surface. When the temperature was higher than 1000 °C, a severe reduction in strength was observed. The reliability of the composite material was also improved significantly by such exposures.