Quantifying adherence of oxide scales on steels exposed to high temperature and pressure steam

Oxide scale exfoliation is a major concern in fossil fuel power generation because it can cause tube blockages and erode valves and steam turbine components downstream. There is still considerable scientific and commercial interest to improve the mechanistic understanding of oxide failures by developing models to predict exfoliation and the extent of tube blockage as a function of operating conditions and component geometries. Tensile testing inside a scanning electron microscope was conducted on ferritic–martensitic and austenitic steel specimens with the steam side (Fe,Cr)-rich oxides grown after exposures for up to 1000 h in steam with ~100 ppb O₂ at 276 bar and 550°C. Multiple oxide layer cracks and delamination events were observed and analyzed in detail during the tests. Results from the testing agreed well with earlier observations that had identified the failure location at the outer–inner oxide layer for all tested materials. Calculated adhesion energies identified the outer–inner oxide interface of alloy 347HFG as the weakest interface.     

Investigation on steam oxidation behaviour of TP347H FG Part 1: Exposure at 256 bar

The stainless steel TP347H FG is a candidate material for the final stage tubing of superheater and reheater sections of ultra supercritical boilers operated at steam temperatures up to 620°C in the mild corrosion environments of coal‐firing. A series of field tests has been conducted with the aforementioned steel in coal‐fired boilers and this paper focuses on the steam oxidation behaviour for specimens tested at various metal temperatures for exposure times of 7700, 23000 and 30000 hours as investigated by light optical and scanning electron microscopy. The oxide present on the specimens is a duplex oxide, where the outer layer consists of two sub‐layers, an iron oxide layer and an iron‐nickel oxide layer; the inner layer is chromium rich chromium‐iron‐nickel oxide. Microstructure examination showed that for all these samples the varying grain size of subsurface metal affected the oxide thickness, where the larger the metal grain size, the thicker the oxidation scale. This gave the appearance of uneven inner oxides with a varying pit thickness. Comparison of the pit thickness measurement and oxide composition reveals that the oxidation rate is fast during the initial oxidation stage, but the subsequent growth of oxide from further exposure is slower due to the formation of a healing layer consisting of chromium rich oxide near original alloy grain boundaries. At a temperature region above 600°C a thin oxide rich in chromium and manganese is sometimes formed. In addition precipitation of secondary carbides in the bulk metal also occurs at this temperature region.     

Fireside Corrosion of Superheater Materials in Coal/Biomass Co-fired Advanced Power Plants

A series of laboratory-based fireside corrosion exposures were conducted to assess the effect of such conditions on superheater/reheater materials at higher than conventional metal temperatures. Controlled atmosphere furnaces combined with the “deposit recoat” test method were used to generate the exposure conditions; the gaseous environment simulated that anticipated from air-firing 20 wt% cereal co-product mixed with a UK coal. The exposures were carried out at 600, 650 and 700 °C with four candidate materials: T92, HR3C and 347HFG steels; nickel-based alloy 625. After the exposures, the samples were examined by SEM/EDX to characterize the damage. Pre- and post-exposure dimensional metrology were used to quantify the metal damage in terms of metal loss distributions. For the austenitic steels, the combined deposit/gas/temperature exposure conditions enabled quantification of the characteristic ‘bell-shaped’ curves (of damage as a function of temperature) for fireside corrosion.     

高温服役后TP347HFG钢的组织与性能

利用金相显微镜、SEM、EDS和万能试验机分析了过热器管TP347HFG钢高温运行1.2×10⁴ h和7.5×10⁴ h后的组织与性能。结果表明,高温服役1.2×10⁴ h和7.5×10⁴ h后,TP347HFG钢仍保持明显的孪晶特征,析出的NbC有利于保持材料的组织稳定性。TP347HFG钢高温服役后力学性能能够保持稳定,随服役时间增加,强度增加而塑性变化不大。     

Laboratory corrosion tests for simulating fireside wastage of superheater materials in waste incinerators

Laboratory corrosion tests were performed to clarify the effects of relative amounts of fused salts in tube deposits on corrosion rates of superheater materials in WTE plants. All test exposures were at 550 °C and of 100 h duration. The nine synthetic ashes used as corrodents consisted of mixtures of chlorides, sulfates and oxides. The test materials were alloy steel T22, stainless steels TP347H, TP310HCbN, and alloys HR11N and 625. The gas atmosphere consisted of 500 to 3000 ppm HCl‐30 ppm SO₂‐10% O₂‐10% CO₂‐20% H₂O‐bal.N₂. Generally, the relative amount of fused salts in non‐fused ash constituents at 550 °C increased with increasing the chlorine content of the ashes. The corrosion rate of T22 steel did not depend directly on ash chlorine content, but for ashes of 7.7 wt.% Cl, the corrosion rate depended on the calculated amount of fused salt at 500 °C. The corrosion rates of TP347H steel and alloy 625 were maximum for ashes of 6–8 wt.% Cl. For ashes of 7.7 wt.% Cl, the corrosion rates of T22 steel, stainless steels, and alloys increased with ashes having higher amounts of fused salts. Increased HCl content of the gas caused higher corrosion of the stainless steels and high‐nickel alloys, but there was no clear corrosion‐exacerbating effect with T22 steel.     

C和Nb含量对TP347HFG钢在650℃析出相参量和持久寿命的影响

研究了C和Nb含量对TP347HFG钢在650℃析出相参量（成分、体积分数和尺寸）和持久寿命的影响.对ASME成分范围内的2种不同C和Nb含量的TP347HFG钢在650℃,230和150 MPa条件下进行持久实验,持久寿命分别为199,420 h和2426,8837 h,其中C含量较低Nb含量较高的样品持久寿命较长.对持久管样的EPMA-EDS+MPSM和TEM-EDS分析表明,较低的C含量和较高的Nb含量对应较少的M₂₃C6和较多的MX,并阻碍了M₂₃C₆的聚集粗化,同时基体中可保留较多的Cr,有利于延长持久寿命.此外,运用热力学软件Thermo-Calc分析了在500—1300℃范围内C和Nb组合含量的变化对各相成分和体积分数的影响,与实验结果相吻合.     

C和Nb含量对TP347HFG钢在650℃析出相参量和持久寿命的影响

研究了C和Nb含量对TP347HFG钢在650℃析出相参量（成分、体积分数和尺寸）和持久寿命的影响.对ASME成分范围内的2种不同C和Nb含量的TP347HFG钢在650℃,230和150 MPa条件下进行持久实验,持久寿命分别为199,420 h和2426,8837 h,其中C含量较低Nb含量较高的样品持久寿命较长.对持久管样的EPMA-EDS+MPSM和TEM-EDS分析表明,较低的C含量和较高的Nb含量对应较少的M₂₃C₆和较多的MX,并阻碍了M₂₃C₆的聚集粗化,同时基体中可保留较多的Cr,有利于延长持久寿命.此外,运用热力学软件Thermo-Calc分析了在500-1300℃范围内C和Nb组合含量的变化对各相成分和体积分数的影响,与实验结果相吻合.     

TP347H钢高温水蒸气氧化研究

研究了在600MW超临界机组屏式过热器TP347H管运行5000h后的高温蒸气氧化层。通过分析蒸气氧化层成分、相结构以及Cr的分布,并结合高温水蒸气存在的情况下氧化膜生长速度,提出了高温蒸气氧化层的形成机理。由Cr的扩散探讨了晶粒尺寸对TP347H管抗高温蒸气氧化性能的影响。结果表明:CrO2(OH)2的挥发导致了外层Fe的氧化物的形成,FeCr2O4内层的形成能够有效减缓蒸气氧化进程,进入稳态氧化阶段后氧化层厚度将保持不变;同时,随晶粒尺寸的减小TP347H的抗蒸气氧化性能提高。     

Steam oxidation and surface hardness of power plant valve materials under the ultra super critical steam condition

Current supereritical steam power plants operate at 3,600 psi and 1,000°F. If the steam temperature is raised from 1,000 °F (538 °C) to 1,150 °F (621°C), the efficiency increases by 2%. Therefore, study on the high temperature corrosion of power plant materials under ultra-superciritical conditions (USC) is necessary to protect the plant from corrosion. In this study, valve materials of 17% Cr martensitic steels (17Cr steel), Incoloy 901 (1901) and their surface nitrided specimens were exposed to USC of 621 °C and 3600 psi (255 kg/cm²) steam for 200 °C, 400 °C, and 800 h. The oxidation of both 17Cr steel and 1901 under the USC for 800 h is very small due to the formation of a protective thin oxide layer formation on the surface. The USC oxidation of both nitrided specimens were increased due to the decomposition and formation of active nitrogen from the non protective nitrides such as Fe₄N, Fe_2–3N, and CrN. The oxidation of nitrided 17Cr steel (n17Cr steel) is about two times higher compared to nitrided 1901 (n1901). The surface hardness is improved by more than two times near the surface by nitriding, and the degradation of hardness by USC oxidation is rapid for n17Cr steel, but slow for n1901.     

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.     

Beitrag zur Kenntnis der Lotsprödigkeit einiger Kupfersorten und Legierungen sowie zweier hochlegierter Stähle

A contribution towards the understanding of liquid metal embrittlement of some coppers, copper alloys and two high-alloy steels The tendency to liquid metal embrittlement in the following materials has been investigated: Three varieties of pure copper, two age-hardenable copper alloys, an extruded brass, an 18/8 stainless steel and a 12% chromium steel. The specimens were exposed to each of the following two commercially available brazes: L-Ag 15 P between 660 and 800°C, and L-Ag 42 Cd between 600 and 750°C. During the tests the brass remained totally unembrittled, whereas the 12% chromium steel was only slightly embrittled in the L-Ag 42 Cd at high temperature. All other materials failed the exposure tests. At the normal brazing temperature the less aggressive solder L-Ag 15 P produced intercrystalline attack only of the 18/8 stainless steel.     

Inconel 617 and Stellite 6 alloys for tooling in thixoforming of steels

Thermal fatigue and high temperature wear are the two principle failure mechanisms for thixoforming dies. Samples of Inconel 617 and Stellite 6 alloys were submitted to thermal cycling under conditions which approximate thixoforming of steels and to sliding wear tests at 750 °C. The experimental results thus obtained were compared with those of the X32CrMoV33 hot work tool steel. The Inconel 617 and Stellite 6 samples are much more resistant to oxidation and to softening than the hot work tool steel, providing a superior resistance to thermal fatigue cracking. The wear resistance of the Inconel 617 and Stellite 6 alloys at 750 °C is also markedly superior. The adhesive oxides growing slowly on Inconel 617 and Stellite 6 alloys sustain the wear action without spalling and are claimed to be responsible for the superior wear resistance of these alloys at 750 °C.     

Microstructural and electrochemical characterisation of heat-treated 347 stainless steel with different phases

Type 347 stainless steel was solution annealed at three different temperatures (1100, 1250 and 1300 °C) followed by ageing at 650 and 750 °C. This was done to study the phase transformations that may occur in stainless steel 347 during welding and/or subsequent ageing. The microstructural examination showed chromium carbide and σ phase formation at the grain boundaries after ageing. The electrochemical behaviour was evaluated by double-loop electrochemical potentiokinetic reactivation test and anodic polarisation in HCl solution. Chromium carbide precipitation caused large increase in the degree of sensitisation, while σ phase had the major effect in decreasing the pitting resistance.     

Investigation of steam oxidation behaviour of TP347H FG. Part 2: Exposure at 91 bar

Tube specimens of TP347FG were exposed in a test superheater loop in a biomass plant in Denmark. The specimens were exposed to surface metal temperatures in the range of 455–568°C, steam pressure of 91 bar and exposure duration of 3500 and 8700 hours. The oxide thickness and morphology was investigated using light optical and scanning electron microscopy. The oxide present on the specimens is a duplex oxide with an inner chromium rich oxide and an outer iron rich oxide. The inner oxide consisted of a primary iron chromium nickel oxide in the original alloy grain and a chromium rich oxide, “healing layer”, at the grain boundaries. This gave the appearance of uneven inner oxide and it was clear that the varying subsurface grain size affected inner oxide thickness, especially after longer exposure times. Longer exposure times from 3500 to 8700 hours resulted in increased pit thickness. Comparison of pit thickness revealed that increase of temperature from 455 to 525°C increases the oxidation rate, however a further increase in temperature did not result in thicker inner oxide presumably due to the formation of a better healing layer at grain boundaries. These results are compared with the previous paper where the pressure and temperature was higher. A thicker inner oxide is observed at the lower temperatures and pressures compared with higher temperatures and pressures. Reasons for this behaviour are discussed.     

Corrosion behavior of various steels in the simulated fluidized bed boiler environment

The corrosion behavior of various austenitic stainless steels and high-alloy steels has been studied in simulated fluidized bed boiler environment to develop a new corrosion resistant austenitic stainless steel for the superheater tube. The superheater is usually not installed within the bed position, which is different from the evaporator installed within the bed position. Therefore, the superheater tubes are exposed to an oxidizing environment; but it is also necessary to estimate the corrosion resistance of the steels in a reducing environment. It is already known that the high temperature corrosion behavior in conditions where CaSO₄ is coated on the steels is more important than the erosion of the superheater tubes. The main results in this present study are as follows: The Nb bearing steels and low C steels showed good resistance to high-temperature corrosion in CaSO₄/CaO, e.g. 347, 304L and HR3C. The corrosion rate of all steels used increased with increase in temperature, particularly at temperatures higher than 650°C. Internal penetration was not detected at temperatures lower than 550°C, but it was detected at temperatures higher than 600°C, in particular, higher than 650°C. The corrosion thickness loss was almost the same as the internal penetration depth at 700 and 750°C in the 300 series steels placed in CaSO₄/CaO, including the fine grained 347 steel, while the internal penetration depth was larger than the corrosion thickness loss in high-alloyed materials such as Alloy 800 and 310 steels. At temperatures higher than 800°C, the same result was also obtained for the fine grained 347 steel. The corrosion during exposure to oxidizing or reducing gases without CaSO₄/CaO or CaS was slight, but when the test specimens were placed in CaSO₄/CaO or CaS, the corrosion rate sharply increased, regardless of the atmospheric gas composition. Cr, Si, Mn (less than 5 %), Mo and Nb are beneficial elements while C, Cu and Al are harmful elements. From the above results, the following steel was developed for high temperature corrosion resistance in CaSO₄/CaO: low C-22/25Cr-17/25Ni-3/5Mn-(2Mo)-Nb-0.08/0.2N-Al-(B).     

Einfluß der β/α-Umwandlung und der ZrV2-Ausscheidung bei Zirkonium-Vanadium-Legierungen auf das Korrosionsverhalten im Sattdampf

Influence of the β-α-transformation and the ZrV₂-precipitation on the corrosion behaviour of ZrV alloys in saturated steam The corrosion behaviour of ZrV alloys with vanadium contents up to 3.5% exhibits a pronounced dependence an heat treatment. In saturated steam of 350° C the weight increase is highest for as-quenched samples. Oxidation follows a linear kinetic law, but already after 5 days bubbles and cracks appear in the oxide layer. Specimens annealed at 450° C exhibit a corrosion behaviour improving with increasing annealing duration. The same is true with annealing at 600° C. The specimens annealed at 750° C exhibited poorer corrosion resistance, but the influence of the duration of treatment was not very pronounced in this case. The Kinetic law is identical for worked and non-worked specimens of the same structure. Non-worked specimens, however, are characterized by increased corrosion susceptibility because of the precipitation of impurities at the primary grain boundaries in the as-cast condition; break-away sets in at an earlier stage in these cases. The external characteristic feature of increasing corrosion is an increasing yellowing of the oxide layer which points to increasing incorporation of variation ions in the oxide layer.     

Niobium carbo-nitride precipitation behavior in a high nitrogen 15Cr-15Ni heat resistant austenitic stainless steel

A high nitrogen 15Cr-15Ni niobium-stabilized austenitic alloy has been produced and subjected to a special heat treatment consisting of 5 hours of solution treatment at 1270 °C followed by hot rolling, quenching and subsequent aging at temperatures of 700 °C to 800 °C. It was found that fine dispersion of nano-sized thermally stable primary Nb(C,N) precipitates had already formed in the as-cast condition. The particles were presented at all examined stages of the TMT process (as-homogenized, as-solution treated and as-aged conditions). Secondary precipitates Nb(C,N) were densely formed during subsequent aging; these precipitates had sizes of 4 nm to 5 nm. Both the primary and secondary Nb(C,N) particles showed excellent thermal stability within the temperature range of 700 °C to 800 °C. The creep properties of the studied alloy at 750 °C were superior when compared to those of commercial type 347 stainless steel.     

Performance of Detonation Gun-Sprayed Ni-20Cr Coating on ASTM A213 TP347H Steel in a Boiler Environment

Detonation gun-sprayed coatings are known for their high density, high bond strength, moderate substrate heating, superior surface finish, better wear/corrosion resistance, and low cost. In this study, detonation gun-spraying technique was used to deposit Ni-20Cr coating on a commonly used boiler steel ASTM A213 TP347H. The specimens with and without coating were subjected to cyclic oxidation testing at an elevated temperature of 700 °C in actual boiler environment to ascertain the usefulness of the coating. The mass change technique was used to establish the kinetics of erosion-corrosion. XRD and SEM/EDS techniques were used to analyze the exposed samples. The uncoated sample suffered from erosion, and a significant mass loss was recorded. It was observed that overall mass loss was reduced by 83% and thickness loss by 53% after the application of the coating. The detonation gun-sprayed Ni-20 Cr coating was found to be suitable to impart erosion resistance to the given steel in the actual boiler environment.     

Steam oxidation and its potential effects on creep strength of power station materials

The oxidation behaviour of several commercial alloys in simulated steam was investigated and compared with that of model alloys with systematic variations of selected alloying elements in the temperature range of 550°C to 650°C. Also, creep tests of specimens pre‐oxidized in steam or in flue gas were carried out in order to study the interaction between creep and corrosion. The corrosion products were characterised by optical microscopy, XRD, SEM/EDX and Raman spectroscopy. It was found that the oxidation resistance of the materials increased with increasing chromium content. High chromium materials exhibited the best oxidation behaviour, whereas the low chromium materials formed thick, multilayered oxide scales, prone to spallation. Anomalous temperature dependences were found in materials with intermediate chromium contents. Creep tests showed a significant reduction in the creep strength of both alloys was caused by a 1000 h thermal exposure treatment at 650°C for P92 and at 800°C for Alloy 800. An additional, though much smaller reduction in strength was observed for the specimens that had been oxidized for 1000 h at 650 or 800°C prior to testing. Further testing is required for confirmation of this effect.     

T91/TP347HFG异种钢焊接接头裂纹原因分析

火电厂高温过热器用T91+TP347HFG异种钢焊接接头运行时,发生开裂泄露。分别从未开裂和开裂部分的焊接接头处取样,采用金相显微镜、扫描电镜、显微硬度计等对焊接接头试样进行检测和对比研究,分析其开裂原因。结果表明:焊接和焊后热处理工艺不当导致T91侧热影响区位置在整个焊接接头区域脆性较大,并有淬硬倾向比较大的组织出现;同时由于焊接规范参数较大而导致焊接热影响区较宽,在一定应力下的作用导致裂纹从此处萌生和扩展,最终导致该异种钢焊接接头开裂失效。