Isothermal oxidation behavior and mechanism of a nickel-based superalloy at 1000℃

The oxidation behavior of a nickel-based superalloy at 1000℃ in air was investigated through X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy analysis. A series of oxides, including external oxide scales (Cr₂O₃, (TiO₂ + MnCr₂O₄)) and internal oxides (Al₂O₃,TiN), were formed on the surface or sub-surface of the substrate at 1000℃ in experimental still air. The oxidation resistance of the alloy was dependent on the stability of the surface oxide layer. The continuity and density of the protective Cr₂O₃ scale were affected by minor alloying elements such as Ti and Mn. The outermost oxide scale was composed of TiO₂ rutile and MnCr₂O₄ spinel, and the growth of TiO₂ particles was controlled by the outer diffusion of Ti ions through the pre-existing oxide layer. Severe internal oxidation occurred beneath the external oxide scale, consuming Al and Ti of the strength phase γ' (Ni₃(Al,Ti)) and thereby severely deteriorating the surface mechanical properties. The depth of the internal oxidation region was approximately 35 μm after exposure to experimental air at 1000℃ for 80 h.     

镍基合金CMSX-4在3.5wt.% NaCl溶液中的腐蚀行为

研究二代镍基合金CMSX-4在质量分数为3.5% NaCl溶液中的腐蚀行为,对该类合金在海洋性环境条件下的应用具有深远意义。通过动电位极化方法研究室温条件下镍基合金CMSX-4在3.5 wt.% NaCl溶液中的电化学行为,利用扫描电子显微镜（SEM）、能谱分析仪（EDS）和X射线光电子能谱仪（XPS）对合金表面阳极腐蚀产物进行微观形貌观察及成分分析。研究表明,CMSX-4合金具有一定的钝化能力,钝化区间比较宽广;在镍基合金CMSX-4表面上形成的腐蚀产物可大致分为两层,表层主要由Ni （OH）₂、Cr （OH）₃、Co （OH）₂和Al （OH）₃等氢氧化物组成,内层主要分布着NiO、Al₂O₃、CoO、Cr₂O₃和CrO₃等氧化物及组成合金基体的各种金属;由Ni （OH）₂和Cr （OH）₃等氢氧化物组成的腐蚀产物膜外层能够在腐蚀介质和金属之间产生较好的屏蔽效果;构成腐蚀产物膜内层的NiO、Al₂O₃、Cr₂O₃和CrO₃等氧化物有利于产物膜内层与外层之间建立一定的空间电荷区,对稳定腐蚀产物内层有很大帮助。研究表明CMSX-4合金在海洋性环境中具有一定的耐蚀性能。     

镀锡钢板铬酸盐钝化膜的X射线光电子谱分析

使用X射线光电子能谱(XPS)全元素扫描分析方法对镀锡钢板铬酸盐钝化膜的成分进行了分析研究.结果表明,组成钝化膜的主要元素为Cr,O,Sn和C.通过Ar+溅射对钝化膜进行深度剖析表明,C元素来自于表面的污染而不是膜层本身;Cr和O元素随着Ar+溅射的进行含量逐渐降低,而Sn元素的含量却逐渐增加.溅射约360 s后,Sn元素的含量已达到了80%以上,此时所对应的钝化膜的厚度约为20 nm.通过窄幅扫描对钝化膜的相组成进行了分析,结果表明钝化膜主要由Cr(OH)3,Cr2O3,Sn及其氧化物构成.     

Preparation of Cr2O3 precursors by hydrothermal reduction in the abundant Na2CO3 and Na2CrO4 solution

Precursors of chromium oxide (p-Cr₂O₃) were prepared by reducing hexavalent chromium in the presence of sodium carbonate solution under hydrothermal conditions. Methanal was used as the reductant, and carbon dioxide was the acidulating agent. The influences of reaction temperature, initial pressure of carbon dioxide, isothermal time and methanal coefficient on Cr(VI) reduction were investigated. Experimental results showed that Cr(VI) was reduced to Cr(III) with a yield of 99%. Chemical titration, thermogravimetry (TG), X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM) were used to characterize the p-Cr₂O₃ and Cr₂O₃. The series of p-Cr₂O₃ were found to be multiphase even if they presented different colors, from gray green to lavender. After these p-Cr₂O₃ samples were calcined, the product of rhombohedral Cr₂O₃ with a purity of 99.5wt% was obtained.     

Oxidation behavior of in-situ Al2O3/TiAl composites at 900°C in static air

In-situ Al₂O₃/TiAl composites were successfully synthesized from the starting powders of Ti, Al, TiO₂ and Nb₂O₅. The oxidation behavior of the composites at 900°C in static air was investigated. The results indicate that the composite samples present a much lower oxidation mass gain. Under long-time intensive oxidation exposure, the formed oxide scale is multi-layer. The formation of the outer TiO₂ layer is fine and dense, the internal Al₂O₃ scale has good adhesiveness with the outer TiO₂ scale, and the TiO₂+Al₂O₃ mixed layer forming the protective oxide scale is favorable for the improvement of oxidation resistance. It is believed that the incorporation of Al₂O₃ particulates into the metal matrix decreases the coefficient of thermal expansion of the substrate, and forms a local three-dimensional network structure that can hold the oxide scale. The formation of the oxide scale with finer particle size, stronger adherence, less micro-defects and slower growth rate can contribute to the improvement of oxidation resistance. Nb element plays an important role in reducing the internal oxidation action of the materials, restraining the growth of TiO₂ crystals and promoting the stable formation of the Al₂O₃-riched layer, which is beneficial to improve the oxidation properties.     

Influence of target-substrate distance and sputtering power on chromium oxide films prepared by medium-frequency magnetron sputtering

Chromium oxide films were deposited on Si (100) substrates by medium-frequency (MF) unbalanced magnetron sputtering at different target-substrate distances D _TS (60, 100, 120 mm) and sputtering power (2.8, 5.6, 11.2 kW), respectively. The structure, surface morphologies, and microhardness of the chromium oxide films were examined by X-ray diffraction (XRD), atomic force microscopy (AFM), and microhardness tester. The results indicate that elevated MF sputtering power can improve the crystallization of the films; The D _TS value affects the structure of the films by changing the preferential orientation from CrO₃ (221) to Cr₂O₃ (116); The microhardness of the chromium oxide films is found to increase with the sputtering power. For preparing the Cr₂O₃-dominated films with comparatively high-performance, the optimized condition is the target-substrate distance of 100 mm and MF sputtering power of 11.2 kW.     

High-throughput synthesis of oxidation-resistant Nb–Si based alloy thin film by magnetron co-sputtering

A high-throughput method was applied to study oxidation behavior of Nb–Si based alloy using composition spread alloy film as combinatorial libraries. An extended range of composition gradients of Nb–Si based alloy film was deposited by (multi)magnetron co-sputtering. The as-deposited film was composed of amorphous phase. Cr₂Nb, Nb₅Si₃ and Nb_ss could be detected after annealing treatment. After oxidation at 1250 ?°C for 10 ?min and 20 ?min, the film composition space was divided into three regions of the distinct oxide scales. The compositions for establishment of the different oxides on Nb–Si based alloy was defined efficiently across the entire composition space by the combinatorial libraries.     

Burn-resistant behavior and mechanism of Ti14 alloy

The direct-current simulation burning method was used to investigate the burn-resistant behavior of Ti14 titanium alloy. The results show that Ti14 alloy exhibits a better burn resistance than TC4 alloy (Ti–6Al–4V). Cu is observed to preferentially migrate to the surface of Ti14 alloy during the burning reaction, and the burned product contains Cu, Cu₂O, and TiO₂. An oxide layer mainly comprising loose TiO₂ is observed beneath the burned product. Meanwhile, Ti₂Cu precipitates at grain boundaries near the interface of the oxide layer, preventing the contact between O₂ and Ti and forming a rapid diffusion layer near the matrix interface. Consequently, a multiple-layer structure with a Cu-enriched layer (burned product)/Cu-lean layer (oxide layer)/Cu-enriched layer (rapid diffusion layer) configuration is formed in the burn heat-affected zone of Ti14 alloy; this multiple-layer structure is beneficial for preventing O₂ diffusion. Furthermore, although Al can migrate to form Al₂O₃ on the surface of TC4 alloy, the burn-resistant ability of TC4 is unimproved because the Al₂O₃ is discontinuous and not present in sufficient quantity.     

Oxidation behavior of the Fe-36Al-0.09C-0.09B-0.04Zr alloy at 1250°C

To explore and study the Fe-Al system alloy presenting exceptional oxidation resistance at high temperature, the Fe-36Al-0.09C-0.09B-0.04Zr alloy was designed and developed. The microstructure and hardness of the backing at 1250°C were analyzed and measured. Thermodynamics and kinetics of the oxidation behavior were also analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques. The results show that the microstructure of the Fe-36Al-0.09C-0.09B-0.04Zr alloy is FeAl phase at ambient temperature and is stable at 1250°C. It displays the excellent property of oxidation resistance because the oxide film has only the Al₂O₃ layer, and its oxidation kinetics curve obeys the parabolic law at 1250°C. The oxidation mechanism at 1250°C is presumed that in the early oxidation period, the alloy oxidizes to form a large number of Al₂O₃ and a little Fe₂O₃, then, the enrichment of Al caused by Fe oxidization combines with O to form Al₂O₃.     

Mesoporous fibrous silicon nitride by catalytic nitridation of silicon

The catalytic effect of metal oxide/alumina whiskers(CeO_2, Mn_3O_4, NiO, Co_3O_4, Fe_2O_3, Cr_2O_3/AW) was evaluated on their ability to drive the nitridation of silicon and to generate mesoporous fibrous silicon networks.Silicon powder with different particles size along with the catalyst was nitridized at 1300 °C for 5 h in nitrogen and nitrogen diluted with 10 vol% ammonia atmospheres. Nitridation degree of silicon up to 99% was recorded using 1.5 wt% CeO_2 and Fe_2O_3 catalysts in nitrogen-ammonia atmosphere. The catalyzed samples contain submicronic silicon nitride fibres with a diameter of 400–500 nm and a length of up to few micrometers. The compressive strength of 46 ± 1 MPa was measured for silicon samples catalyzed with nickel oxide/alumina whiskers and nitridized in N_2/10 vol%NH_3 atmosphere. Porous silicon nitride networks were produced with 45–52% porosity, pore sizes in the range of 370–1200 nm and median pore in the range of 495–1655 nm.     

Crystalline mesoporous metal oxide

Since the discovery of many types of mesoporous silicas, such as SBA-15, KIT-6, FDU-12 and SBA-16, porous crystalline transition metal oxides, such as Cr2O3, Co3O4, In2O3, NiO, CeO2, WO3, Fe2O3 and MnO2, have been synthesized using the mesoporous silicas as hard templates. Several synthetic methods have been developed. These new porous materials have high potential applications in catalysis, Li-ion rechargeable batteries and gas sensors. This article gives a brief review of the research of porous crystals of metal oxides in the last four years.     

Wear properties of NiAl based materials

The NiAl based materials including NiAl-TiC-Al2O3 composite,NiAl-Cr(Mo)-Hf-Ho eutectic alloy and NiAl-Cr(Mo)-CrxSy in situ composite were fabricated and their wear properties were tested at different temperatures.The results revealed that the NiAl-TiC-Al2O3 composite,NiAl-Cr(Mo)-Hf-Ho eutectic alloy and NiAl-Cr(Mo)-CrxSy in situ composite exhibited the excellent wear properties between 700℃ and 900℃.The microstructure observations exhibited that the self-lubricant films formed on the worn surfaces during the dry sliding test at high temperature,which decreased the wear rate and friction coefficient significantly.TEM observation on the self-lubricant film revealed that it was mainly comprised by ceramic amorphous and nanocrystalline.Compared with the NiAl-TiC-Al2O3 composite,the NiAl-Cr(Mo)-CrxSy in situ composite has lower friction coefficient at low temperature.Such phenomena may be ascribed to the addition of sulfide which contributes much to the formation of self-lubricant,and moreover the TiC addition increase the strength of NiAl based material and its wear resistance.     

Chemical quenching and inhibition of positronium in Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The pore structure of Cr2O3/Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity I3 keep nearly unchanged. The Doppler broadening S parameters also show sharp decrease with increasing Cr2O3 content. Detailed analysis of the CDB spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o-Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensity I4 indicates that Cr2O3 also inhibits positronium formation.     

Corrosion behavior of ferritic ODS steel prepared by adding YH_2 nanoparticles in supercritical water at 600 °C

The corrosion behavior of the ferritic oxide dispersion strengthened(ODS)steel(14Cr-3Al-2W-0.1Ti)prepared by adding YH_2nanoparticles(NPs)was investigated in supercritical water(SCW)at 600°C for 1500 h.The mass gain of the ODS steel(215.5 mg/dm~2)was lower than that of SUS430 steel(357.2 mg/dm~2).A dual oxide layer generated on the surface of ODS steel after corrosion in SCW.The outer layer was composed of Fe_2O_3and Fe_3O_4,while the inner layer composed of the spinel-type FeCr_2O_4together with Al_2O_3.The generation of Y_2Ti_2O_7NPs in the ODS steel by adding YH_2NPs prohibits the formation of Y-Al-O particles and leaves more Al available to form a continuous protective oxide scale to improve the corrosion resistance.Moreover,the Y_2Ti_2O_7NPs act as efficient barriers to suppress the outward diffusion of metal atoms.This novel ODS steel shows potential applications in supercritical water.     

Investigation of the deterioration of passive films in H<Subscript>2</Subscript>S-containing solutions

The effect of H₂S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO₂ to H₂S and then back to CO₂. The presence of H₂S showed an acceleration effect on the corrosion of 316L stainless steel in comparison with CO₂. The acceleration effect remained even after the complete removal of H₂S by CO₂, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr₂O₃, Fe₂O₃, and FeS₂ after being immersed in H₂S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott-Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

抗脱落铁基二氧化铅电极的研究

采用3步阳极氧化法在铁片表面依次生成铁氧化膜、β-PbO₂和α-PbO₂，制得结合牢固、抗脱落性能优良、具有 Fe/Fe_xO_y/β-PbO₂/α-PbO₂结构的铁基二氧化铅电极。采用XPS、XRD、交流阻抗和扫描电镜对铁氧化膜组成、β-PbO₂和α-PbO₂的晶型及电化学活性、电极切面结构进行了分析表征。借鉴漆膜性能标准测试方法，对铁基二氧化铅镀层的抗机械脱落性能进行了综合测试评价。研究发现，预先将铁基体放在4 mol/L KOH水溶液中，在温度80℃、阳极电流密度60mA/cm²条件下，使铁片表面预氧化生成一层棕红色的Fe₃O₄薄膜，然后再依次阳极氧化电镀β-PbO₂和α-PbO₂，能够获得抗机械脱落性好、电化学反应活性高的铁基二氧化铅电极。     

铸造镍基高温合金K35的氧化动力学

用静态增重法研究了K35镍基铸造高温合金的800℃氧化动力学·结果表明,K35合金的氧化动力学遵循抛物线规律,属于完全抗氧化级·利用X射线衍射、扫描电镜和能谱分析确定K35合金氧化膜组成以Cr2O3为主,含有NiCr2O4及TiO·TiO2·由于钛氧化物的存在,在高温氧化期间,K35合金发生了内氧化·     

Graded bandgap semiconductor thin film photoelectrodes

A graded bandgap oxide semiconductor thin film electrode was designed in order to obtain a photoelec-trochemically stable photoelectrode, with wide absorption range. The graded bandgap Ti_1−x V _x O₂ film electrode was prepared by heating the stacked layers of V/Ti in varying ratios, which were coated on the substrate by the sol-gel method using the starting solution with various V/Ti ratios. XPS result showed that the composition gradient was achieved for the film. The Ti_1−x V _x O₂ film electrode was found to be photoelectrochemically stable. Its photovoltage was about 360 mV. Obvious visible light photoresponse was observed for the Ti_1−x V _x O₂ film electrode. Compared with the pure TiO₂ electrode, the photocurrent onset potential of the Ti_1−x V _x O₂ film electrode was shifted positively, probably because the accumulation of vanadium at the electrode surface causes the recombination of the electrons and holes, and the lowest level of the conduction band of Ti_1−x V _x O₂ is lower than that of TiO₂. Impedance analysis showed that the donor density of the Ti_1−x V₂O₂ film electrode was higher than that of TiO₂ film electrode.     

SUS441不锈钢/Al金属间化合物微叠层复合板的界面结构与力学性能

采用“表面预处理—交替层叠—热轧复合—热处理”的工艺流程制备了SUS441不锈钢/Al金属间化合物微叠层复合板。利用光学显微镜、X射线衍射仪、扫描电子显微镜等检测与表征方法研究了热处理温度对复合板界面形貌、微观组织、物相组成、维氏硬度、拉伸性能的影响。结果表明：复合板界面结合良好;热处理后,固–液反应界面氧化严重,易导致界面分层而开裂;固–固、固–半固、固–液热处理后,金属间化合物层由均匀层和两相层组成,均匀层的物相组成为Fe₂A1₅,两相层的物相组成为Fe₄Al₁₃和Al₁₃Cr₂,且两相层具有韧性特征,固–半固反应所得到的复合板的综合力学性能最佳。     

Preparation and properties of the Ni-Al/Fe-Al intermetallics composite coating produced by plasma cladding

A novel approach to produce an intermetallic composite coating was put forward. The microstructure, microhardness, and dry-sliding wear behavior of the composite coating were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrum (EDS) analysis, microhardness test, and ball-on-disc wear experiment. XRD results indicate that some new phases FeAl, Fe_0.23Ni_0.77Al, and Ni₃Al exit in the composite coating with the Al₂O₃ addition. SEM results show that the coating is bonded with carbon steel metallurgically and exhibits typical rapid directional solidification structures. The Cr₇C₃ carbide and intermetallic compounds co-reinforced composite coating has a high average hardness and exhibits an excellent wear resistance under dry-sliding wear test compared with the Cr₇C₃ carbide-reinforced composite coating. The formation mechanism of the intermetallic compounds was also investigated.