Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle (Teil II)

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels (Part II) Austenitic stainless steel (18% Cr, 12% Ni, Mo gradation between 0,06 to 3,6%) had been solution nitrided. By step‐by‐step removing, the samples could be prepared with various surface contents of nitrogen from 0.04 to 0.42%. In two test series the influence of nitrogen had been determined. The susceptibility against pitting corrosion of these samples had been tested by the chronopotentiostatical method. For the investigated steel composition and the used corrosion system there is no infuence of molybdenum on the effectiveness of nitrogen. The effectiveness of nitrogen can be described by the factor 25 in the PRE. By the investigation of the surfaces with the XPS analysis, it could be shown that the passivation and the pit nucleation is influenced by nitrogen. In these ranges NO_x, NH_x, and NH_z‐spectra have been detected. Bound Mo was found in steels containing molybdenum. It is assumed that the repassivation mechanisms of N and Mo work independently of each other. With the results efforts are supported to improve the pitting corrosion resistance also at molybdenum poor steels by surface nitriding or nitrogen alloying. The achieved results justify the assumption that the observed positive effect of the nitrogen may be extented to even higher nitrogen contents. A prerequisite for this is avoiding secondary phases in the matrix. The adverse influence of small particles is known well.     

Kinetics of high temperature corrosion of a low Cr‐Mo steel in aqueous NaCl Solution

The kinetics of corrosion of a low Cr‐Mo steel alloy were studied over the temperature range of 75–250°C in 1 m NaCl in absence and in presence of various levels of contamination with CuCl₂. Corrosion rates, weights of corrosion product (magnetite) film and total (integral) weight loss of the alloy over exposure times from 1 up to 480 h were measured. The corrosion rate decreases rapidly with time, before it levels off at longer time, indicating the formation of a protective corrosion product film. The ability of the alloy to retain an adherent corrosion product (magnetite) film was expressed in terms of a retention coefficient. This was found to increase with temperature and exposure time and to decrease with the level of contamination with CuCl₂. This effect of temperature was attributed to the improvement of the crystallinity of the corrosion product. On the other hand, the effect of CuCl₂ was attributed to the electrodeposition of Cu and its impregnation within the corrosion product, which becomes less adherent. The free corrosion potential was found to be affected by the presence of the CuCl₂, in a fashion compatible with the Wagner‐Traud theory of mixed potential.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels Austenitic stainless steels (18% Cr, 12% Ni, Mo gradation between 0.5 to 3.6%) had been gas‐nitrided. By stepwise removal, samples could be prepared with various surface content of nitrogen up to 0.45%. The susceptibility against pitting corrosion of these samples had been tested by two methods: – determination of the stable pitting potential in 0.5 M NaCl at 25°C – determination of the critical pitting temperature in artificial sea water (DIN 81249‐4) The influence of nitrogen to both determined parameter can be described well by PRE = Cr + 3,3 · Mo + 25 · N That means for the investigated steel composition and the used corrosion system there is no influence of molybdenum on the effectiveness of nitrogen.     

Performance of cold sprayed Ni‐20Cr and Ni‐50Cr coatings on SA 516 steel in actual industrial environment of a coal fired boiler

Power plants are one of the major industries suffering from severe erosion–corrosion (E‐C) problems resulting in substantial losses. One way of tackling this problem is by the use of thermal spray coatings. In the current investigation a new emerging technique i.e. cold spray coating process was used to deposit Ni‐20Cr and Ni‐50Cr powder on SA 516 (grade 70) boiler steel. The bare as well as the coated steels were subjected to cyclic experimental studies, in the superheater zone of a coal fired boiler. Weight change, thickness loss, XRD, FE‐SEM/EDS and X‐ray mapping techniques were used to analyse the eroded‐corroded specimens. The uncoated steel showed weight gain after exposure in the actual boiler environment, whereas, for the coated steels there was initial weight loss followed by negligible weight change. Based upon thickness loss data the cold‐sprayed Ni‐50Cr coating was found to provide better E‐C resistance than the Ni‐20Cr coating.     

Corrosion behavior of UCX,KHR35, and KHR45 alloys in molten nitrates

The corrosion behavior of three high-Ni, high-Cr alloys, that is, UCX, KHR35, and KHR45 alloys, in a mixture of 60% NaNO₃–40% KNO₃ at 600°C has been evaluated by using weight loss tests, potentiodynamic polarization curves, and electrochemical impedance spectroscopy measurements. Cr contents ranged between 23.25 and 43.2 wt.%, whereas Ni ranged between 36.6 and 50.3 wt.%. For comparison, the same studies were performed on 304-type stainless steel (304SS). Tests were complemented with detailed scanning electronic microscope and X-ray diffraction studies. Results showed that that the three high-Ni, high-Cr alloys had lower weight loss than that for 304SS. Polarization tests indicated the formation of a passive layer in all cases. Electrochemical impedance spectroscopy data have shown that the corrosion mechanism for all the alloys was charge transfer from the alloy to the molten salt. Finally, X-ray patterns showed the presence of Cr₂O₃ in all tested alloys, which is responsible for the observed passive behavior and their corrosion resistance.     

Oxidation behaviour of Fe‐Cr‐Al alloys during resistance and furnace heating

The behaviour of thin Fe‐Cr‐Al heating element strips was investigated with respect to the oxidation limited life times and geometrical changes during resistance and furnace heating. For this purpose, isothermal and cyclic oxidation tests varying in their total exposure time and cycle duration were performed in the temperature range 1050–1200 °C. Specimens subjected to rapid cyclic, resistance heating revealed shorter life times than calculated for specimens subjected to isothermal exposure. The life times were found to increase with increasing cycle duration and hence decreasing number of cycles for a given time at temperature. This life time decrease is related to an “hour glass” waviness of the specimens, which develops during prolonged thermal cycling. The development of this plastic deformation also occurred during furnace heated, thermal cycling tests. A two‐step mechanism is introduced combining an oxidation kinetics related time to the onset of significant waviness with an enhancement of this waviness as a result of a ratcheting effect. The latter seems to strongly depend on the number of cycles and on the plastic deformation generated during each cycle rather than on the total time at temperature. The development of an “hour glass” waviness leads to an enhanced aluminium depletion due to an increase of the specimen surface area. Additional deformation phenomena like “hot tube” or “corkscrew” behaviour occur during the resistance heating tests. These are related to a temperature gradient that develops over the specimen width due to the poor aspect ratio of the specimens.     

KCl‐induced corrosion of Ni‐based alloys containing 35–45 wt% Cr

Ni–(35–45)Cr–4Nb alloys containing different fractions of α‐Cr were exposed to potassium chloride (KCl)‐induced corrosion. The corrosion exposures were carried out for 168 hr at 600°C in a 15% (vol/vol) H₂O (g) + 5% (vol/vol) O₂ (g) + N₂ (g; balance) atmosphere using KCl‐free (reference) and predeposited KCl samples. To mimic the KCl deposition in real boilers, 24 hr exposures where KCl vapor condensed continuously onto samples were also performed. The corrosion attack of the studied materials increased significantly when KCl was present compared to the KCl‐free samples. For the KCl exposures, the corrosion attack drastically increased when a significant α‐Cr fraction was present. α‐Cr was either selectively attacked or dissolved through solid‐state diffusion and a layered build‐up of the outer external scale of K₂CrO₄ and chromia could be observed. For the in situ condensed KCl exposure, severe corrosion was observed already within the 24 hr exposure, indicating a higher corrosion rate compared with when KCl was predeposited.     

Corrosion resistant Ti alloy for sulphuric acid medium: Suitability of Ti–Mo alloys

The corrosion resistance of Ti–Mo (5, 10, 15 and 25 wt% molybdenum) alloys in 5–25% sulphuric acid was evaluated. The Ti–Mo alloys offered a better corrosion resistance than commercially pure titanium (CP‐Ti). The higher impedance values, higher phase angle maximum, ability to reach the phase angle maximum at relatively lower frequencies, ability to exhibit a constant phase angle maximum over a wider range of frequencies, higher phase angle values at 0.01 Hz, have confirmed the formation of a stable passive oxide film on Ti–Mo alloys. The study recommends the use of Ti–Mo alloys, particularly Ti–25Mo alloy, as a suitable material of construction for sulphuric acid medium.     

1Cr5Mo钢高温应力腐蚀及防护方法的研究现状

针对1Cr5Mo钢的性能特点及应用情况,综述了当前1Cr5Mo钢热处理工艺、焊接及腐蚀防护等方面的研究进展,提出了研究及实际应用过程中存在的问题,并对未来的研究方向及热点进行了展望.     

Corrosion resistance of Ni‐50Cr HVOF coatings on 310S alloy substrates in a metal dusting atmosphere

Metal dusting attack has been examined after three 168 h cycles on two Ni‐50Cr coatings with different microstructures deposited on 310S alloy substrates by the high velocity oxy‐fuel (HVOF) thermal‐spray process. Metal dusting in uncoated 310S alloy specimens was found to be still in the initiation stage after 504 h of exposure in the 50H₂:50CO gas environment at 620 °C. Dense Ni‐50Cr coatings offered suitable resistance to metal dusting. Metal dusting was observed in the 310S substrates adjacent to pores at the interface between the substrate and a porous Ni‐50Cr coating. The porosity present in the as‐deposited coatings was shown to introduce a large variability into coating performance. Carbon formed by decomposition of the gaseous species accumulated in the surface pores and resulted in the dislodgement of surface splats due to stresses generated by the volume changes. When the corrosive gas atmosphere was able to penetrate through the interconnected pores and reach the coating–substrate interface, the 310S substrate was carburized, metal dusting attack occurred, and the resulting formation of coke in the pores led to local failure of the coating.     

Long‐term exposure of austenitic steels and nickel‐based alloys in lignite‐biomass cofiring

The aim of this study was to assess the long‐term impact that the addition of biomass provokes on superheater materials exposed to fireside corrosion environments. Alloys covering a broad range of commercially available materials were investigated. Their corrosion kinetics under different corrosive deposits and atmospheres was evaluated, and their corrosion products analyzed to deepen understanding of the underlying corrosion mechanisms. Therefore, three nickel‐based alloys and three austenitic steels containing 20–24 wt.% Cr were tested at 650°C for 7,000 hr. The long‐term exposure shows new mechanistic aspects of Type II hot corrosion that were revealed by accelerated material depletion. The formation of Ni–NiS eutectic and the formation of a Cr depleted zone close to the substrate corrosion product interface are indicative of the breakaway occurrence. Differences in the corrosion behavior are related to the balance of Ni, Mo, Co, and Cr and can serve as the material selection argument. The evaluation concluded with the finding that alloys presenting Mo and Ni might be preferentially used in fireside corrosion in the presence of biomass, whereas the use of austenitic steels suffer less corrosion if no biomass is present in the corrosive atmosphere.     

Corrosion behavior of Ti‐xNb‐13Zr alloys in Ringer's solution

Ti‐6Al‐4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V‐free alloys and both V‐ and Al‐free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti‐13Nb‐13Zr alloy is promising due to its better biomechanical compatibility than Ti‐6Al‐4V. In this work, the corrosion behavior of Ti, Ti‐6Al‐4V, and Ti‐xNb‐13Zr alloys (x = 5, 13, and 20) was evaluated in Ringer's solution (pH 7.5) at 37 °C through open‐circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10^?7 A/cm²) and high impedance values (in the order of 10⁵ Ωcm² at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti‐xNb‐13Zr alloys were more corrosion resistant than both Ti and Ti‐6Al‐4V in Ringer's solution.     

Oxidation mechanisms of Cr‐containing steels and Ni‐base alloys at high‐temperatures –. Part I: The different role of alloy grain boundaries

It is essential for materials used at high‐temperatures in corrosive atmosphere to maintain their specific properties, such as good creep resistance, long fatigue life and sufficient high‐temperature corrosion resistance. Usually, the corrosion resistance results from the formation of a protective scale with very low porosity, good adherence, high mechanical and thermodynamic stability and slow growth rate. Standard engineering materials in power generation technology are low‐Cr steels. However, steels with higher Cr content, e.g., austenitic steels, or Ni‐base alloys are used for components applied to more severe service conditions, e.g., more aggressive atmospheres and higher temperatures. Three categories of alloys were investigated in this study. These materials were oxidised in laboratory air at temperatures of 550°C in the case of low‐alloy steels, 750°C in the case of an austenitic steel (TP347) and up to 1000°C in the case of the Ni‐base superalloys Inconel 625 Si and Inconel 718. Emphasis was put on the role of grain size on the internal and external oxidation processes. For this purpose various grain sizes were established by means of recrystallization heat treatment. In the case of low‐Cr steels, thermogravimetric measurements revealed a substantially higher mass gain for steels with smaller grain sizes. This observation was attributed to the role of alloy grain boundaries as short‐circuit diffusion paths for inward oxygen transport. For the austenitic steel, the situation is the other way round. The scale formed on specimens with smaller grain size consists mainly of Cr₂O₃ with some FeCr₂O₄ at localized sites, while for specimens with larger grain size a non‐protective Fe oxide scale is formed. This finding supports the idea that substrate grain boundaries accelerate the chromium supply to the oxide/alloy phase interface. Finally, in the Ni‐base superalloys deep intergranular oxidation attack was observed, taking place preferentially along random high‐angle grain boundaries.     

Corrosion behavior of nanostructured Ni‐Si3N4 composite films: A study of electrochemical impedance spectroscopy

Ni‐Si₃N₄ nanocomposite films with both the consecutive Ni crystallites and dispersed Si₃N₄ particles in the nanometer range have been fabricated using DC electroplating technique, and characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), and X‐ray diffraction (XRD). The corrosion resistance of the Ni‐Si₃N₄ nanocomposite film has been compared to that of pure Ni coating through polarization. Meanwhile, the corrosion process of Ni‐Si₃N₄ nanocomposite film in neutral 3.5% NaCl solution has been investigated using electrochemical impedance spectroscopy (EIS). The results show that the Ni‐Si₃N₄ nanocomposite film is more resistant to corrosion than the pure Ni coating. The corrosion of Ni‐Si₃N₄ nanocomposite film is controlled by electrochemical step, and the whole corrosion process is divided into two sequential stages. The main corrosion type of Ni‐Si₃N₄ nanocomposite films in neutral 3.5% NaCl solution is pitting.     

焊接对00Cr22Ni5Mo3N筒体耐蚀性的影响及工艺优化

对00Cr22Ni5Mo3N双相不锈钢简体主焊缝焊接后耐蚀性能下降的原因进行了分析;通过焊接试验研究,总结出该材料焊接的优化工艺及专项技术措施,为现场顺利制造设备及提高一次性返修合格率积累了经验,对类似材质结构装备的焊接亦有积极的指导作用。     

Metal dusting behaviour of welded Ni‐base alloys with different surface finish

Welded Ni‐base alloys and Alloy 800 were exposed under metal dusting conditions at 600°C and 650°C for up to 6000 hours. Alloy 800 was attacked very strongly already in the first days and Alloy 600 also rather soon and widespread, on both materials attack started mainly in the heat affected zone. Several surface states of Alloy 600: brushed, ground, sand‐blasted and pickled were tried only grinding caused a modest delay and decrease of metal dusting attack. Generally the attack was less widespread but deeper at 650°C than at 600°C, also for Alloy 601 and 602. The latter alloys show minor, mainly local attack, but especially the welds are affected. TIG welding led to better resistance than hand‐welding.