Air Oxidation of Ni–Ti Alloys at 650–850°C

The oxidation of pure Ni and three Ni–Ti alloys containing 5, 10, and 15 wt.% Ti over the temperature range 650–850°C in air was studied to examine the effect of titanium on the oxidation resistance of pure nickel. Ni–5Ti is a single-phase solid solution, while the other two alloys consisted of nickel solid solution (-Ni) and TiNi₃. The oxidation of Ni–Ti alloys at 650°C follows an approximately parabolic rate law and produces a decrease in the oxidation rate of pure Ni by forming an almost pure TiO₂ scale. At higher temperatures, Ni–Ti alloys also follow an approximately parabolic oxidation, and their oxidation rates are close to or faster than those of pure Ni. Duplex scales containing NiO, NiTiO₃ and TiO₂ formed. Some internal oxides of titanium formed, especially at 850°C. In addition, the two-phase structure of Ni–10Ti and Ni–15Ti was transformed into a single-phase structure beneath the scales.     

The corrosion behavior of two-phase Ni-Dy alloys in a eutectic (Li,K)2CO3 mixture at 650 °C

The corrosion behavior of binary Ni-Dy alloys containing 1, 3 and 5 wt.% Dy in a eutectic (0.62Li,0.38K)₂CO₃ mixture at 650 °C has been investigated. The alloys are two-phase composed of α-Ni solid solution and intermetallic compound Dy₂Ni₁₇. The experimental results indicate that the corrosion rate of the three Ni-Dy alloys is significantly lower than that of pure Ni, forming a scale mainly composed of NiO together with a small amount of dysprosium oxides. The weight gain of the alloys changes little with the content of dysprosium, while the thickness of the scale decreases with increasing content of dysprosium. The presence of Dy can promote the lithiation process of NiO during immersion in the melt. The corrosion mechanism of the alloys is also discussed.     

The corrosion of two NiNb alloys under 1 atm O2 at 600–800 °C

The oxidation of two NiNb alloys containing 15 and 30 wt% Nb has been studied at 600–800 °C in pure oxygen under 1 atm O₂ at 600–800 °C. The scales formed on both alloys under all conditions show an external scale, generally duplex, containing an outermost layer of nearly pure NiO and an innermost region of NiO mixed with the double NiNb oxide NiNb₂O₆. Moreover, the samples corroded at all temperatures also show a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb₂O₅ or/and NbO₂), which formed from both alloy phases Ni₈Nb and Ni₃Nb. No important depletion of niobium was observed in the alloy close to the interface with the zone of internal oxidation, while the depth of this region is generally much higher than measured for the corrosion of the same alloys under low oxygen pressures at the same temperatures. The corrosion mechanism of these alloys is examined with special reference to the effects of the low solubility of niobium in nickel.     

The corrosion behavior of Ni-Nb alloys in a mixed gas of H2-H2O-H2S

The corrosion behavior of Ni-Nb alloys containing up to 40 wt.% Nb was studied over the temperature range of 550–800°C in a mixed H₂/H₂O/H₂S gas. The scales formed on all alloys were multilayered. The outer scale was single-phase Ni₃S₂, while the structure and constitution of the inner scale depended on alloy composition and reaction conditions. Internal oxidation has been found in Ni-20Nb and Ni-30Nb, external oxidation has been observed on Ni-34Nb. Platinum markers were located at the interface between the outer scale and inner scale. The decrease in corrosion rate with increasing Nb content may be attributed to the presence of increasing amounts of Ni-Nb double sulfides as well as to the presence of Nb₂O₅ in the inner region of the scale.     

The corrosion behavior of Ni-Al alloys and Ni-Nb-Al alloys in a H2/H2O/H2S gas mixture

The corrosion behavior of two Ni-Al alloys and four Ni-Nb-Al alloys was studied over the temperature range of 600° C to 1000° C in a mixed-gas of H₂/H₂O/H₂S. The parabolic law was generally followed, although linear kinetics were also observed. Multiple-stage kinetics were observed for the Ni-Al alloys. Generally, the scales formed on Ni-13.5Al and Ni-Nb-Al alloys were multilayered, with an outer layer of nickel sulfide with or without pure Ni particles and a complex inner scale. The outer scale became porous and discontinuous with increasing temperature. Very thin scales formed on Ni-31Al. The reduction in corrosion rate with increasing Al content is ascribed to the formation of Al₂O₃ and Al₂S₃ in the scale. Platinum markers were found at the interface between the outer and inner scales.     

The corrosion behavior of Ni-Mo alloys in a H2/H2O/H2S gas mixture

The corrosion behavior of Ni-Mo alloys containing up to 40 wt.% Mo was studied over the temperature range of 550–800C in a mixed gas of H₂/H₂O/ H₂S. The scales formed on all alloys contained only sulfides and were doublelayered. The outer scale was single-phase Ni₃S₂. Depending on the alloy composition and reaction conditions, the inner scale was: (1) a mixture of MoS₂ plus Ni₃S₂ with/without Ni, (2) MoS₂, or (3) MoS₂ plus intermetallic particles and/or double sulfide Ni_2.5Mo₆S_6.7. Neither internal oxidation nor internal sulfidation were observed at lower temperatures. Internal sulfidation was however observed at higher temperature when the scale apparently melted. The parabolic law was generally obeyed for the most concentrated alloys. For the two more-dilute alloys the kinetics were mostly linear. A decrease in the corrosion rate occurred with increasing Mo content of the alloy and may be attributed to the presence of increasing volume fractions of MoS₂ and/or of a double Ni-Mo sulfide in the inner region of the scale. For the two most concentrated alloys this may also be due to the presence of a number of particles of the unsulfidized intermetallic compound, which is Ni₃Mo for Ni-30Mo, but NiMo for Ni-40Mo.     

阳极氧化法制备TiO2膜在模拟深海热液区的耐腐蚀性能

以恒压阳极氧化方法在钛基体上制备TiO₂氧化膜,使用水热釜模拟深海热液区的条件研究其耐腐蚀性能。采用XRD、SEM、接触角测定仪对氧化膜以及腐蚀试样产物进行晶型、表面结构、化学成分和亲疏水性能测定,使用动电位扫描方法对其进行极化曲线测试。结果表明,钛试样和阳极氧化钛试样在模拟深海环境条件下,经过腐蚀反应在表面都生成了一层非致密的TiO₂ 膜,对基体并不能起到保护作用,而阳极氧化生成的致密TiO₂ 膜对基体能够起到很好的保护作用。经腐蚀后钛试样表面有TiH₂相的形成,腐蚀电位负移0.45 V。而阳极氧化钛试样表面没有TiH₂相的形成,且腐蚀电位负移较小,表现出良好的耐腐蚀性能。     

Investigation on the corrosion and oxidation resistance of Ni-Al2O3 nano-composite coatings prepared by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique from a Watt's type electrolyte containing nano-Al₂O₃ particles. The corrosion resistance and high temperature oxidation resistance of resulting composite coatings were investigated. It was found that the incorporation of nano-Al₂O₃ particles in Ni matrix refined the Ni crystal and changed the preferential orientation of composite coatings. Meanwhile, the corrosion and oxidation resistance were improved after the incorporation of nano-Al₂O₃ particles into Ni matrix. The nano-Al₂O₃ content in deposits plays an important role for improving the corrosion and oxidation protection. The corrosion and oxidation resistance of Ni-Al₂O₃ nano-composite coatings produced via SCD technique are superior to that of CEP technique. Compared to pure Ni and Ni-Al₂O₃ composite coatings fabricated using CEP technique, the Ni-7.58 wt.% Al₂O₃ composite coating obtained by SCD technique exhibits better corrosion resistance and enhanced high temperature oxidation resistance. Moreover, the mechanism of corrosion and high temperature oxidation resistance of Ni-Al₂O₃ nano-composite coatings are discussed.     

Oxidation Behavior of Ni-3,6, 10 wt.% Al Alloys at 800°C

The oxidation behavior of Ni and Ni-3, 6, and 10Al alloys at 800°C in an N₂–O₂ gas mixture was investigated. The mass gain of each alloy depended on both the oxidation periods and Al content. NiO scale was formed on all alloy substrates accompanied by internal oxides of Al₂O₃. Many cavities were formed at the NiO/substrate interface at shorter oxidation times, and these cavities were found to be filled by metallic Ni(Al) from the matrix in the internal-oxidation zone by the development of internal oxides. The filling of cavities by Ni(Al) was more significant on higher Al alloys, which had a higher density of internal Al₂O₃. Once metallic Ni(Al) formed along the entire NiO/substrate interface, the oxidation kinetics became the same as pure Ni. It was concluded that pure Ni filling the cavities at the interface provided a diffusion path of Ni from the substrate to the NiO scale, and that controlled the oxidation kinetics.     

High temperature scaling of Ni-xSi-10 at.% Al alloys in 1 atm of pure O2

The oxidation of Ni-xSi-10Al alloys (with x = 0, 2, 4 and 6 at.%), has been studied at 900 and 1000 °C in 1 atm of pure O₂ to examine the effect of different silicon additions on the behavior of ternary Ni-Si-10Al alloys. The kinetic curves of Ni-10Al are approximately parabolic at both 900 and 1000 °C. Conversely, the kinetics of the ternary alloys at both temperatures correspond generally to a rate decrease faster than predicted by the parabolic rate law, except for the oxidation of Ni-6Si-10Al at 1000 °C, which exhibits a single nearly-parabolic stage. Oxidation of the binary alloy formed at both temperatures an internal oxidation zone beneath a layer of NiO. Oxidation of Ni-2Si-10Al at both temperatures and of the other two alloys at 900 °C formed initially a zone of internal oxidation of Al + Si. However, a layer of alumina forming at the front of internal oxidation after some time blocked the internal oxidation and produced a gradual conversion of the metal matrix of this region into NiO, with a simultaneous decrease of the oxidation rate. Conversely, the oxidation of Ni-4Si-10Al and Ni-6Si-10Al at 1000 °C did not produce an internal oxidation, but formed an alumina layer directly on the alloy surface after an initial stage when also Ni was oxidized. Therefore, silicon exerts the third-element effect by reducing the critical Al content needed for the transition from its internal to its external oxidation with respect to the corresponding Ni-Al alloy. This result is interpreted by means of an extension to ternary alloys of Wagner’s criterion for the same transition in binary alloys based on the attainment of a critical volume fraction of internal oxide.     

Oxidation Behavior of Ni-3, 6 wt% Al Alloys at 800 °C in Atmospheres Containing Water Vapor

The oxidation behavior of Ni, Ni–3Al, and Ni–6Al alloys at 800 °C in air + H₂O was investigated. The oxidation kinetics of Ni and the alloys in air + H₂O were very similar, but the mass gains of Ni and each alloy were smaller in air + H₂O than in air. Oxidation products formed on Ni-3 and 6Al alloys consisted of an outer NiO scale and internal Al₂O₃ precipitates. The growth rates of both NiO and the internal oxidation zone were much smaller in air + H₂O. The NiO scale formed in air + H₂O was duplex in structure with outer porous and inner dense layers. The outer porous layer consisted of fine powder-like NiO particles. A thicker metallic Ni(Al) layer formed at the NiO/alloy interface in air + H₂O, caused by extrusion of Ni from the substrate due to volume changes accompanying the internal oxide formation. Formation of the metallic Ni layer appeared to be the reason for the similarity between the oxidation kinetics of both Ni and the alloys in air + H₂O.     

Ba0.5Sr0.5TiO3铁电薄膜的微弧氧化成膜研究

以0.2 mol/L Ba(OH)2+0.2 mol/L Sr(OH)2溶液为电解液,采用微弧氧化法,在Ti板表面原位生长铁电薄膜,并对薄膜的物相构成、元素分布情况、截面结构及介电性能进行表征。结果表明:该工艺下制备的薄膜主要由四方相Ba0.5Sr0.5TiO3构成,薄膜致密层内,Ba,Sr,Ti和O元素分布都较均匀,但在微弧氧化孔洞附近存在含量波动;该薄膜在1 kHz下的介电常数较优,为411.3。最后对微弧氧化沉积铁电薄膜的成膜过程进行了分析,提出了微弧氧化过程中可能存在的化学反应。     

Protective and non-protective scale formation of NiCr alloys in water vapour containing high- and low-pO2 gases

The oxidation behaviour of NiCr alloys with Cr contents of 10, 20 and 25 wt.%, respectively, were studied in Ar-O₂, Ar-O₂-H₂O and Ar-H₂O mixtures. TG and SEM analysis revealed that the chromia scales formed on Ni-25Cr in the wet gases did not differ substantially from those formed in Ar-O₂. For the two “borderline” alloys Ni-10Cr and Ni-20Cr, addition of water vapour to Ar-O₂ hampered the formation of a protective chromia scale which, especially for Ni-10Cr, resulted in substantially increased scale growth rates compared to exposures in dry gas. Different from numerous observations described in the literature for “borderline” FeCr alloys with intermediate Cr contents of 10-20%, the corresponding NiCr alloys showed in Ar-H₂O a smaller tendency for non-protective scale formation than in Ar-O₂-H₂O. This is caused by the decreasing growth rate of NiO with decreasing pO₂ of the test gas, with the secondary effect that external chromia scale formation is promoted in low-pO₂ gases such as Ar-H₂O. Even if the alloy Cr content was too low to obtain external chromia scale formation, the oxidation rate in Ar-H₂O would, in contrast to low-Cr FeCr alloys, be quite small due to the very slow growth rate of NiO in this low-pO₂ gas.     

Electrochemical stability of TiO2 nanotubes with different diameters in artificial saliva

Recently, titanium and titanium alloys with nanotube layers by anodizing process have gained great interests as surgical implant materials. In this present paper, their electrochemical stability of self-organized TiO₂ nanotubue layers prepared by anodization of pure Ti in 0.5 wt.% hydrofluoric acid has been investigated in simulated biological environment by use of open-circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The electrochemical testing results indicate that the nanotubular Ti with the diameter of TiO₂ nanotube lower than 86 nm shows a better corrosion resistance in artificial saliva than that of the mechanically polished Ti. Moreover, the electrochemical stability of Ti nanotubes 22 to 59 nm in diameter is improved but that of Ti nanotubes larger than 86 nm decreases. Besides, the corrosion attack of the nanotubular Ti is shown by the collapse of TiO₂ nanotubue layer. The results suggest that the electrochemical corrosion behavior of nanotubular Ti in artificial saliva is related to the diameter of the nanotubes and thickness of the barrier layer.     

The oxidation of three Ni-6Si-xAl alloys in 1 atm O2 at 1000 °C

The oxidation of three ternary Ni-6Si-xAl alloys containing 6, 10 and 15 at.% Al and of the corresponding binary Ni-Al alloys has been studied at 1000 °C under 1 atm O₂ to examine the effect of different Al additions on the behavior of ternary Ni-Al-Si alloys containing 6 at.% Si. Of the three binary Ni-Al alloys only Ni-15Al was able to form external alumina scales. Conversely, all the three ternary alloys formed an innermost layer of alumina directly in contact with the alloy following very similar and approximately parabolic kinetics after a short faster initial stage due to transient formation of NiO. Thus, the presence of silicon is very effective to reduce the critical Al content needed to form exclusive alumina scales with respect to binary Ni-Al alloys. The third-element effect due to silicon is interpreted on the basis of an extension of Wagner’s criterion for the transition from the internal to the external oxidation of the most reactive component in binary alloys.     

The oxidation of two ternary Ni-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of the ternary alloys Ni-45Cu-10Al and Ni-30Cu-10Al has been studied at 800-900 °C under 1 atm O₂. The presence of 10 at.% Al reduces significantly the oxidation rate of the corresponding Cu-Ni alloys during the initial oxidation stages, even before the establishment of a complete Al₂O₃ layer. The weight of individual sample of the two ternary Ni-Cu-10Al alloys at 800 °C increases more rapidly than at 900 °C during the initial oxidation stage. As oxidation proceeds, the weight gain at 800 °C slows down to a degree that the total weight gain after 24 h oxidation at 800 °C is less than that at 900 °C. Due to a faster formation of the Al₂O₃ layer, which suppresses earlier the further oxidation of Cu and Ni, the external region of the scales grown on Ni-45Cu-10Al contain much less Cu and Ni oxides than those grown on Ni-30Cu-10Al. The transition from the internal oxidation to the selective external oxidation of the most reactive component Al in Ni-Cu-Al alloys is favored by higher values of the Al content, of temperature and of the Cu/Ni ratio.     

Effect of internal oxidation pretreatments and Si contamination on oxide-scale growth and spalling

Internal oxidation pretreatments carried out in quartz capsule with a Rhines pack were found to have a profound effect on the subsequent oxidation behavior of alloys. Specimens of Co-15 wt.% Cr, Co-25 wt.% Cr, Ni-25 wt.% Cr, and Ni-25 wt.% Cr-1 wt.% Al were tested at 1100°C after pre-oxidation treatments. Even without the development of internal oxide particles, pretreated binary CoCr and NiCr alloys oxidized with significantly lower rates. Selective oxidation of chromium was observed on the non-Cr₂O₃-forming Co-base alloys, whereas on the Cr₂O₃-forming Ni-base alloys, elimination of base-metal oxide, reduction in the Cr₂O₃ growth rate, and better scale adhesion were found. These effects were more apparent with pre-oxidation temperatures greater than 1000°C and with longer pretreatment times. Contaimination of Si from the quartz is believed to be the cause.     

TiO2纳米阵列超疏水膜的制备及耐腐蚀性能

采用阳极氧化法在纯钛表面制备TiO2纳米管阵列,使用六甲基二硅胺烷对TiO2纳米管阵列进行低表面能处理,得到超疏水表面．用接触角测量仪测定表面疏水性,采用SEM、EDS技术研究改性前后试样表面的形貌和元素组成,并利用极化曲线和电化学阻抗谱法研究了超疏水膜的耐腐蚀性能．结果表明,TiO2纳米管阵列经改性后超疏水效果明显,...     

氧化参数对TiO_2纳米管结构及双室光电化学池产氢性能的影响

采用乙二醇电解液,在不同氧化电压、氧化时间条件下通过阳极氧化纯钛片制备了一系列TiO_2纳米管阵列薄膜。使用场发射扫描电镜(FESEM)表征TiO_2纳米管的表面、断面形貌,探讨氧化时间及氧化电压对纳米管生长速率的影响。同时通过电化学方法测试TiO_2纳米管的光电化学性能,以无外加电压下双室光电化学池中的产氢量考察其光催化活性。结果表明,相比延长氧化时间,提高氧化电压更容易获得高长/径比的TiO_2纳米管阵列,同时可显著提高TiO_2纳米管的光电流、光电转换效率及产氢量。     

A TEM study of the oxide scale development in Ni-Cr-Al alloys

In the present study the isothermal oxidation behaviours of Ni-10Cr-5Al, Ni-20Cr-5Al and Ni-30Cr-5Al alloys were investigated. The alloys were oxidised in air for 50 h at 1000 °C. Analytical transmission electron microscopy was used to characterize the morphology, structure and composition of the oxide scale. The oxide formed adjacent to the alloy was α-Al₂O₃ such that the higher was the Cr content of the alloy the easier was its formation. The Ni-30Cr-5Al alloy formed a complete layer of α-Al₂O₃ in the initial stages of oxidation through ‘oxygen gettering’ by Cr. A decrease in scale thickness and an increase in scale adherence were observed with an increase in Cr content from 10 to 30 wt.%.