High temperature interaction of Al/Si-modified Fe-Cr alloys with KCl

The corrosion behaviour of pure iron, pure chromium, and aluminium/silicon alloyed Fe-Cr materials was investigated at 650 °C in air accompanied by gaseous or solid KCl salt. The corrosion rates of these materials with KCl salt are high and they are strongly affected by the salt amount, the types of the alloying elements and the concentration of chromium. The dominant degradation mechanism for the chromia-forming alloys by KCl attack is the preferential formation of potassium chromate over the conventionally protective chromia, characterized by typical features of bubbles, cracks, volatility and severe spallation for the corrosion products. A detrimental effect of chromium is confirmed. Al-alloying addition to Fe-Cr alloys is beneficial by enhancing the corrosion resistance. Silicon is more effective in promoting the corrosion resistance of Fe-Cr alloys by forming a stable and dense oxide layer in the inner zone which suppresses the rapid growth of iron oxides.     

High-temperature oxidation of Fe-Cr alloys in wet oxygen

Fe-Cr binary alloys have been oxidized in a stream of oxygen containing different amounts of water vapor at 900–1000°C to study the effects of water vapor. The Fe-Cr alloys exhibit an initial protective behavior due to formation of a Cr-rich scale and followed by a nonprotective breakaway oxidation due to formation of iron-rich scale. The appearance of the breakaway oxidation was very sensitive to the water vapor content in the atmosphere. The higher the water vapor content, the earlier the breakaway oxidation takes place. Increasing the oxidizing temperature or decreasing the Cr content in the alloys facilitate an earlier breakaway oxidation. The breakaway oxidation was inhibited effectively by surface-applied CeO₂ particles before oxidation. The oxide scales were examined and analyzed by optical metallography, X-ray diffraction, SEM, and EPMA. A mechanism of the effects of water vapor has been proposed.     

The oxidation of Fe-Cr surface and bulk alloys at 300°C

The oxidation behavior of several surface and bulk Fe-Cr alloys and iron at 300°C and 4×10^–6 Torr oxygen was studied. The surface alloys were fabricated by implantation of 25 keV Cr ions into the outermost 300Å of polycrystalline iron samples. The oxide thickness as a function of oxygen exposure was obtained using proton-excited X-ray analysis, and composition profiles of oxide films were obtained using Auger electron spectroscopy and ion sputtering. The addition of Cr to Fe by surface and bulk alloying caused the oxidation rate to decrease and changed the oxidation kinetics from parabolic (for Fe) to logarithmic (for Cr concentrations 4.7at.%). Interpretation of the data in terms of simple oxidation theories indicates that the Cr additions may reduce the oxidation rate by altering the electronic properties of the metal-oxide interface.     

Effects of water vapour on isothermal oxidation of chromia-forming alloys in Ar/O2 and Ar/H2 atmospheres

Fe9Cr, Fe17Cr and Fe25Cr alloys were subjected to isothermal oxidation in Ar/O₂ and Ar/H₂ atmosphere at 700 °C as high temperature corrosion for 48 h. Oxidation weight change measurement showed increasing Cr content reduced the oxidation rate. The oxidized Cr alloys were analysed using SEM, TEM and XRD. The addition of water vapour accelerates the onset of breakaway oxidation kinetics for Fe9Cr. The presence of water vapour promotes internal oxidation of Cr within Fe9Cr. For Fe17Cr and Fe25Cr, the water vapour effect is not significant due to the large Cr reservoir due to continue growth of Cr₂O₃.     

High temperature corrosion of pure Fe, Cr and Fe-Cr binary alloys in O2 containing trace KCl vapour at 750 °C

Pure Fe, Cr and Fe-Cr binary alloys were corroded in O₂ containing 298 ppm KCl vapour at 750 °C. The corrosion kinetics were determined, and the microstructure and the composition of oxide scales were examined. During corrosion process, KCl vapour reacted with the formed oxide scales and generated Cl₂ gas. As Cl₂ gas introduced the active oxidation, a multilayer oxide scales consisted of an outmost Fe₂O₃ layer and an inner Cr₂O₃ layer formed on the Fe-Cr alloys with lower Cr concentration. In the case of Fe-60Cr or Fe-80Cr alloys, monolayer Cr₂O₃ formed as the healing oxidation process. However, multilayer Cr₂O₃ formed on pure Cr.     

On the influence of water vapour on the oxidation behaviour of pure Ti

The influence of water vapour on the oxidation behaviour of pure titanium in air at 700 °C and 900 °C was evaluated through thermogravimetric tests. The influence of water vapour during oxidation at 700 °C was small, resulting in slightly higher mass gains in the moist atmosphere. At 900 °C, a multilayered rutil scale was developed from the earliest stages of oxidation. In this case, presence of water resulted in a considerable decrease of the oxidation kinetics. It is proposed that water promotes densification of the innermost part of the rutile layer by increasing rutile creep rate.     

Unusual oxidation behaviour of Zr50Cu50 alloy at high temperatures

The oxidation of Zr₅₀Cu₅₀ alloy at 500-700 °C is characterized by preferential oxidation of zirconium, while the excess of copper is accumulated at the alloy-oxide interface forming the Zr₁₄Cu₅₁ phase. The strong reaction at 800 and 850 °C resulted in the total corrosion of the specimens in 21 and 15 h, respectively. The oxidation at elevated temperatures showed an anomalous decrease of the oxygen consumption rate in the temperature range 930-1000 °C, corresponding to the preferentially oriented crystallites of ZrO₂ in the oxide scale at 900 and 1000 °C. The oxide layer consists of ZrO₂ and CuO in the whole temperature interval of the oxidation. The reaction kinetics obeys a parabolic rate law. An activation energy of 92.0 ± 0.3 kJ/mol has been estimated.     

High temperature oxidation mechanism of dilute copper aluminium alloys

Dilute copper-aluminium alloys were oxidized in air from 700 to 1000 °C. Two distinctive behaviours were observed: alloys with at least 3 wt% aluminium showed excellent oxidation resistance in the whole temperature range. Alloys with 2 wt% or less aluminium exhibited good oxidation resistance up to 800 °C; but as the temperature was further increased, the oxidation rate of these alloys increased and became comparable to that of pure copper. A kinetic model was developed to explain the oxidation behaviour and indirectly determine the amount of dissolved oxygen in the alloys tested. It was found that the oxygen dissolved in alloys with up to 2 wt% Al exceeded its solubility limit in copper, whereas the dissolved oxygen in alloys with higher aluminium contents was below the solubility limit. This difference may account for the significantly different oxidation resistance.     

Metal dusting behaviour of Cr-Ni steels and Ni-base alloys in a simulated syngas mixture

Long-term laboratory exposure tests for various Cr and Ni content steels and Ni-base alloys were conducted at 650 °C in a 60vol.%CO-26%H₂-11.5%CO₂-2.5%H₂O gas mixture simulating syngas environments. Upon isothermal heating, alloys with 15% and 20% Cr had many pits on the surface after a brief exposure, while no pit was found on alloys containing of 60% Ni and more than 23% Cr exposed for up to 5000 h. The thermal cycling accelerated pit initiation drastically, resulting that all test specimens except 30%Cr-60%Ni alloy suffered from metal dusting. From a measurement of pit depths, Ni proved to be an effective alloying element to retard the pit growth: growth rate for 75% Ni alloy has achieved double-digit decrease compared to that for 20% Ni. Microscopic observations has revealed that platelet graphite aligned perpendicular at the boundary of gas/metal of pits. The length of the platelet graphite for high Ni alloys was appreciably longer than that for low Ni steels. This can be interpreted from the difference of super saturation of carbon.     

Characterization of microstructures and oxidation behaviour of Nb–20Si–20Cr–5Al alloy

Static oxidation in air was performed on Nb–20Cr–20Si–5Al alloy at high temperatures ranging from 700 to 1400 °C. Pesting occurred at 700 °C while internal oxidation took place at 1300 and 1400 °C where Al₂O₃ initiated at the interface between NbCr₂ and Nb₉Cr₃Si₂ phases. Phases present were Nb₅Si₃, NbCr₂, Nb solid solution and Nb₉Cr₃Si₂ depending on the temperature. The aluminium content on each of the phases was analyzed. Al content in Nb₉Si₂Cr₃ has been found to be as high as 5–6 atomic percent. SEM, EDS and XRD techniques were utilized in order to characterize the specimens.     

Compositional effects of Zr-rich multi-component brazing alloys on the corrosion of Zr alloy joints

High-temperature corrosion of Zircaloy-4 joints brazed by various Zr(Ti)–Cu–Ni-based multi-component alloys was studied to draw up the compositional guideline of the brazing alloy. From the compositional and microstructural effects of the joints on the corrosion, there was strong evidence for galvanic corrosion susceptibility of primary α-Zr grains (usually Sn-containing) owing to alloying of nobler Ti and its concentration gradient in a joint, inducing a microgalvanic corrosion. The Ti concentration for corrosion inhibition was proposed to be less than about 1.0 at.%. The results clearly demonstrate that the exclusion of Ti is needed for the use of Zr-rich multi-component brazing alloys.     

Oxidation behaviour of selected wrought Ni-base high temperature alloys when used as flame tube material in modern blue flame oil burners

Modern blue flame burners are equipped with a flame tube that serves for recirculation of exhaust gas and for flame stabilization. The in operation material temperature, temperature changes and atmospheres at the flame tube have been measured. Exposure tests of four Ni-Cr-alloys with different concentrations of Al have been carried out under these conditions. The breakdown of the material was connected with the failure of the oxide layer and finally with the formation of internal aluminium nitrides. An approach has been developed for predicting the failure of the oxide layer and hence of the life time of the material.     

Microcrack generation and its healing in the oxide scale formed on Fe-Cr alloys

Fe -base alloys containing 5, 10, and 20 wt. % Cr were oxidized in a stream of O₂ at 750 and 900°C up to 264 hr. A sulfur decoration method was applied to detect the cracks generated in the scale during oxidation. This method revealed frequent crack generation and its healing in the scale. In the case of low-Cr alloys, the cracks are filled up with newly formed Fe-rich oxide but may be regenerated during further oxidation. Cracks are generated in the scale on an Fe-20Cr alloy also, although this alloy is not so severely attacked because of rapid healing.     

Anomalous temperature dependence of oxidation kinetics during steam oxidation of ferritic steels in the temperature range 550-650 °C

The oxidation behavior of a number of selected ferritic steels in a simulated steam environment at temperatures between 550 and 650 °C was studied. In the prevailing test gas, some of the studied 9-12% Cr steels tended to exhibit an anomalous temperature dependence of the oxidation behavior. This means, that the oxidation rates do not steadily increase with increasing temperature. At higher temperatures, some of the studied steels tend to form a very thin and protective oxide scale whereas at lower temperature rapidly growing, less-protective oxides are being developed. The anomalous temperature dependence is related to differences in chromium distribution in the inner part of the oxide scale. The effect is observed for steels with intermediate-Cr contents (∼10-12%) whereas steels with either lower or higher Cr contents exhibit an increasing oxidation rate with increasing temperature.     

Field studies of corrosion behaviour of copper alloys in natural seawater

Eight copper alloys were tested in a one-year field deployment in the North Atlantic Ocean. The corrosion behaviour was characterized by weight loss, optical and electronic microscopy analyses. The biofouling performance was quantified in terms of the biomass accumulation. The testing program included specimens in tensioned and untensioned configurations, as well as a set for seasonal deployments. The seasonal corrosion rates were 140% higher, and the rates of tensioned specimens were 39% higher than those of the untensioned specimens after 12 months of deployment. Good biofouling resistance was observed for all but one alloy, which exhibited heavy fouling by barnacles.     

Influence of water vapor on the oxidation behavior of aluminized coatings under low oxygen partial pressure

FeCrNi alloy after aluminizing was oxidized at 1000 °C in dry and humid (2.23 vol.% water) H₂. Experimental results showed that H₂ promotes the formation of θ alumina and its transformation to α alumina. The morphology of surface alumina coating does not change significantly, but the oxidation rate of the aluminized layer accelerates by the addition of water vapor. As a result, more cracks are found beneath the alumina layer when water vapor is present. The addition of water vapor seems having a favorable effect on the selective oxidation of Al and concentration of oxygen vacancy in the aluminized alloys.     

An investigation on oxidation wear mechanisms of Ti-46Al-7Nb-0.7Cr-0.1Si-0.2Ni intermetallic-based alloys

The results of investigation on oxidation wear mechanism of Ti-46Al-7Nb-0.7Cr-0.1Si-0.2Ni-based intermetallic alloy are presented. Oxidation was carried out in air at temperatures: 900 °C, 925 °C and 975 °C taking into account the micro-geometry of surfaces being heated and oxidized. It was determined that the rise of surface roughness to Ra = 5.8 μm definitely reduces scale of chipping in higher temperature (975 °C). Investigation of the material structure of the specimen and chemical composition of oxidation products was performed. Possibilities of an increase in the heat resistance of the tested alloy by means of application of high roughness surfaces were shown.     

氧化时间及铬含量对Fe-Cr钢高温氧化行为的影响

为了测定不同氧化时间以及铬含量对高温条件下钢材表面氧化铁皮组织和厚度的影响,将Fe-5Cr钢与Fe-10Cr钢在1000℃空气条件下氧化60～180 min,采用增重法绘制其氧化动力学曲线,并利用光学显微镜、能谱仪和X射线衍射仪对氧化铁皮的断面形貌和物相进行研究.结果表明,两试验钢氧化初期为气-固反应,中后期为气...     

Effect of dissolved hydrogen on the electrochemical behaviour of Alloy 600 in simulated PWR primary water at 290 °C

With an increase in dissolved hydrogen (DH) content from 0 to 5 cm³ STP H₂/kg H₂O the electrochemical behaviour of Alloy 600 in deaerated PWR primary water at 290 °C was investigated, using corrosion potential (E_corr) monitoring, potentiodynamic polarization, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). DH content controls the E_corr of Alloy 600. Raising DH content directly promotes the cathodic process and reduces the passivity of Alloy 600 significantly. EIS results show that increasing DH content results in a thinner inner-layer oxide film and ions diffusion becomes easier. The mechanism of these DH effects is discussed.     

Corrosion of metals and alloys in molten glasses. Part 2: nickel and cobalt high chromium superalloys behaviour and protection

Electrochemical methods have been used for the characterisation of high chromium alloys corrosion in molten glasses (cobalt and nickel base alloys in a borosilicate glass at 1050 °C, with rotating working electrodes). All the tested alloys are active but passivable materials. The active state is characterised by a rapid dissolution of the constitutive elements of the alloy in the glass melt. The passive state can be obtained by an air oxidation of the alloys (called preoxidation) or with a temporary anodic polarisation of the alloy. The obtained passive state is due to the presence of a thin protective chromia scale.