Oxidation behaviour of some modern heat-resistant cast steels

The kinetics and morphological development of the oxidation of a selection of modern heat-resistant cast steels have been examined and compared with those of the traditional material, HK40. The materials examined had Cr contents of 24 to 29 weight percent (wt %), Ni contents of 30 to 46 wt %and in several cases minority additions of Nb, W, or both. One steel contained 3.3 wt % Al. Kinetics were measured gravimetrically over periods of 6 to 100 h and found to be parabolic in all cases except for the Al-containing steel, which oxidized in an irregular and irreproducible fashion. All steels formed an external scale of Cr₂O₃ with a Mn-rich spinel layer at the outer surface. Beneath this scale was a layer of alloy depleted in both Cr and Mn. Within the depleted layer inter-dendritic carbides had been destroyed, leaving either oxide near the external alloy surface or voids deeper within the alloy.     

Oxidation behaviour in Si-containing low-carbon steels

Oxygen partial pressure at the boundary between external oxidation layer and steel matrix was determined by characterisation of internal oxidation in Si-containing low-carbon steels oxidised under atmospheric condition. The oxygen partial pressure calculated from the rate equation of the internal oxidation matches with the equilibrium value between Fe and FeO. From the oxygen partial pressure between external oxidation layer and steel matrix, the evolution of internal oxidation zone and the diffusion profile of solute Si were numerically simulated. The calculated depth of internal oxidation and solute Si profile accords to the measured ones from the EPMA, which implies that the numerical simulation captures reasonably the evolution of the internal oxidation in the Si-containing steels.     

Oxidation behaviour of steels in advanced gas cooled reactors

Abstract

EDF Energy operates 14 advanced gas cooled reactors (AGRs) in the UK to generate electricity. CO₂ gas is used as the primary coolant in the AGRs, and a range of steels are used as for the structural components: e.g. 9Cr-1Mo ferritic steels and stainless steels. These steels are susceptible to both oxidation and carburisation in CO₂ dominated primary coolant gas under high pressure between 300 and 650 °C. Material degradation is a key concern for lifetime extension of the power stations, and EDF Energy and its predecessors have carried out a series of research programmes to better understand steel oxidation behaviour in AGRs and to develop more realistic lifetime prediction methodologies. These are used to secure safe and reliable operation of the AGRs. In this paper, an overview of oxidation behaviour of steels used in AGRs and some examples from the above programmes are described.     

Static strain ageing behaviour of dual phase steels

In this work an investigation was conducted into the cold deformation ageing susceptibility of a carbon steel and a microalloyed steel, both with dual phase micro-structure. Ageing experiments after different prestrains were carried out at temperatures ranging from 25 to 250 °C. It was found that yield strength (YS) and tensile strength (UTS) of the steels with different dual phase micro-structures exhibit maximum values at ageing temperature of 100 °C after different prestrains. It is assumed that the first rise is based on the formation of solute atom atmospheres around dislocations and the further strengthening in the second step is caused by the low-temperature carbide precipitation in ferrite. When the ageing temperature increased to 150, 200 or 250 °C, YS decreased due to tempering effect in martensite. It was also found that the ageing of the microalloyed steel occurred more slowly than that of the carbon steel. The slow occurrence of ageing was clearly observed at temperatures of 100, 150, 200 and 250 °C and was attributed to the chemical composition of the steels.     

High speed steels for hot rolls with improved impact and thermal fatigue resistance

Abstract

Experimental centrifugally cast high speed steels (HSSs) with a modified solidification microstructure were produced, with the aim of improving impact properties and thermal fatigue resistance to extend the application of these materials to the production of roughing and intermediate finishing hot rolls. On the basis of a Thermo-Calc simulation, the chemical composition was changed to reduce the amount and continuity of the eutectic carbide network. All study materials with such a modified microstructure exhibited a significant increase in the above-mentioned properties with respect to a standard HSS grade used in first finishing stands. This result was obtained by increasing the contents of alloying elements that form proeutectic carbides, and of carbon.     

Microstructure of hot dip coated Fe–Si steels

Hot dipping is a coating technique pre-eminently used in industry to galvanize machine parts or steel sheets for constructional applications. However, other hot dipping applications have been developed in order to have a positive effect on specific material properties. For instance, in Fe–Si electrical steels, a Si/Al rich top layer is applied and followed by diffusion annealing to increase the electrical resistivity of the material and consequently, lower the power losses. Hot dipped aluminised mild steels have been developed with increased corrosion resistance for high temperature applications by the development of a dense Al₂O₃ layer. Regardless of the type of steel coated and the intended application, after the interaction between the molten Al and the solid material, three constituents are formed: Fe₂Al₅, FeAl₃ and an Al-rich alloy. The structural morphology, which can negatively affect the wear resistance and the thermal stability, also appears to be highly dependent on the chemical composition of the base material. To study thermo-mechanical and compositional effects on the coating behavior after hot dipping, cold rolling with different reductions was performed on different Fe–Si materials. It was demonstrated that hardness differences between the layers caused crack formation inside the Fe₂Al₅ layer during subsequent deformation. The present work reports the results obtained on materials that were hot dipped in a hypo-eutectic Al + 1 wt.% Si bath. The bath was used to coat Fe–Si steel substrates with variable silicon content with dipping times ranging from 1 to 20 s. Before dipping, the samples were heated to 700 °C and subsequently immersed in the liquid bath at temperatures of 710 °C, 720 °C and 740 °C. To further evaluate the interactions between Al, Si and Fe, a diffusion annealing treatment at 1000 °C was performed. The main diffusing elements during this treatment are Al and Fe, although small variations in Si content are also observed. At a certain distance from the surface, voids were observed, which most probably can be related to the Kirkendall effect. A characterization of the formed intermetallics was performed by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-Ray Diffraction (XRD) and Electron Backscatter diffraction (EBSD).     

Effect of Nb and C on the hot flow behavior of Nb microalloyed steels

The compressive deformation behaviors of a C–Mn steel (0.36C–1.42Mn) and two Nb microalloyed steels (0.35C–1.41Mn–0.044Nb and 0.055C–1.42Mn–0.036Nb) were investigated at the temperatures from 900 °C to 1100 °C and strain rates from 0.005 s⁻¹ to 10 s⁻¹ on Gleeble-1500 thermo-mechanical simulator. It was found that the flow stress of the C–Mn steel is the lowest among the experimental steels, indicating that Nb microalloying in HSLA steels can effectively increase the hot deformation flow stress, and the 0.055C–1.42Mn–0.036Nb steel has a higher flow stress than that of the 0.35C–1.41Mn–0.044Nb steel, indicating that C addition generates a softening effect. The flow stress constitutive equations of hot deformation were developed for the experimental steels, the activation energy Q about 360 kJ/mol for the 0.055C–1.42Mn–0.036Nb steel was higher than that for the 0.35C–1.41Mn–0.044Nb steel (347 kJ/mol) and the C–Mn steel (278 kJ/mol). Characteristic points of flow stress for the three steels were analyzed. The results showed that Nb addition can effectively increase the peak strain and the steady state strain of steels, thus delay distinctly the occurrence of dynamic recrystallization, while C addition can reduce the peak strain and the steady state strain of Nb microalloyed steels, thus promote the occurrence of dynamic recrystallization.     

Influence of Ti on hot ductility of Nb containing HSLA steels

Abstract

The influence of a low Ti addition (～0·01%) on the hot ductility of Nb containing HSLA steels has been examined. For conventional cooling conditions in which an average cooling rate from the melting point to the test temperature was used, the ductility decreased markedly with the addition of Ti. However, when cooling conditions after melting were more in accord with the thermal heat treatment undergone by the strand during continuous casting, i.e. cooling is fast to begin with, reaches a minimum and then reheats, after which the temperature falls more slowly to the test temperature, the Ti addition was found to be beneficial.     

The creep and fracture behaviour of tempered martensitic steels

Creep strength enhanced ferritic steels contain 9 to 12% Cr and were developed to exhibit excellent high temperature properties. These should be achieved when the microstructure exhibits a tempered martensitic matrix containing a substructure with a high dislocation density and a uniform dispersion of fine, second phase precipitates. It is interesting to note that when properly processed the typical alloy compositions for these steels provide reasonable strength but can exhibit brittle creep behaviour. The levels of ductility required in engineering applications necessitate proper control of composition (including trace elements), steel making and processing and all heat treatments. The properties needed for modern design methods can only be obtained using validated procedures for both uniaxial and multiaxial testing and documentation to establish the mechanisms controlling deformation and fracture for relevant stress states.     

C-SiC-TiC-TiB_2复合材料等温氧化行为研究

对原位合成的（Ｃ－ＳｉＣ－ＴｉＣ－ＴｉＢ２）碳／陶复合材料的等温抗氧化性能进行了研究。结果表明，该材料的氧化增重和失重主要取决于碳相和陶瓷相的氧化速率和氧化层的结构特征。该材料表现出优良的抗氧化能力，这归结于在８００℃时ＴｉＢ２优先氧化，８００～１０００℃时其表面生成了一层致密的硼硅酸盐玻璃，以及在１２００℃下ＴｉＯ２晶粒包裹在其表面。     

Influence of the microstructure on the plastic behaviour of duplex stainless steels

Microstructure change of α (ferrite) + γ (austenite) two-phase structure in duplex stainless steels deformed by hot torsion tests is briefly analyzed. Two types of stainless steels containing different volume fractions of ferrite and austenite were torsion deformed at temperatures ranging from 900 to 1250 °C. Steel A (25.5Cr-4.9Ni-1.6Mo) contained Cr_eq/Ni_eq = 4.8 and steel B (22.2Cr-5.6Ni-3Mo) contained Cr_eq/Ni_eq = 3.5 bring about different microstructures and flow stress behaviour. The results show that the shape of the flow stress curves depends on the material and on deformation conditions. Four different flow curve shapes were observed. At high temperatures, steel A displayed a plastic behaviour typical of ferritic stainless steels. As the deformation temperature decreased, the flow curves presented peak stresses at low-temperature deformation. When the austenite particles are distributed coarsely in the matrix (steel B), the plastic flow curve displays a stress peak separating extensive regions of hardening and softening. When both phases have the same volume fractions, the microstructure is characterized by percolation of the two phases in the samples, and the plastic flow curve takes on a very distinctive shape in hot torsion tests. The role of the microstructure present during deformation on the shape of the flow stress curves is analyzed.     

Influence of B on hot ductility of high Al,TWIP steels

Abstract

The influence of B on the hot ductility of high Al, Ti containing twinning induced plasticity (TWIP) steels has been examined. It was established that provided the B was fully protected by adding sufficient Ti to combine with all the N, then B could segregate to the austenite grain boundaries and improve ductility. This improvement was particularly marked for the temperature range of 700–900°C, the range in which the straightening operation often takes place in continuous casting. Of most importance in the present work has been the detection of B at the boundaries using a secondary ion mass spectrometry technique. The cooling rate from the reheating temperature of 1250°C to the tensile testing temperature range of 700–1200°C was 60 K min^?1, but it is likely that slower cooling rates ≤25 K min^?1, more in keeping with the secondary cooling rate on continuous casting, will give even better ductility. Ti additions in themselves are beneficial to the hot ductility of these steels as precipitation of AlN at the austenite boundaries is avoided, but only if the cooling rate is sufficiently slow to allow the TiN particles to coarsen. However, to ensure freedom from cracking, an addition of B is also required.     

Cr9Mo和Cr5Mo钢的等温氧化行为

对铸态和锻态的Ｃｒ９Ｍｏ和Ｃｒ５Ｍｏ钢分别在７００℃、８００℃和９００℃下进行了为时５００ｈ的氧化试验。结果表明，在７００℃、８００℃下Ｃｒ９Ｍｏ的抗氧化性能比Ｃｒ５Ｍｏ的优越得多，而在９００℃下则相差不多。两种钢的抗氧化性能的差别主要是其表面氧化物性质不同所致。铸态和锻态抗氧化性能的差别则是由于其合金元素分布的均匀度不同，致使氧化物结构有差异造成的。     

自制铁铬锰合金耐液锌腐蚀性能的研究

针对应用于连续热镀锌生产线上辊类部件用材设计的奥氏体合金,系统研究了自制铁铬锰合金在工业锌液中(Zn-0.2%Al)的腐蚀行为及组织变化规律.研究表明:铁铬锰合金在工业锌液中具有良好的耐锌腐蚀能力,其腐蚀速率为8.11×10-4 g/(cm2.h),而316L的腐蚀速率为1.65×10-3 g/(cm2.h);铁铬锰合金在工业锌液中首先生成Fe2Al5,其稳定性较好,可长时间抑制铁锌反应,12 d后铁锌金属间化合物才开始出现,生成的δ(FeZn7)相中,因固溶了质量分数约为5.14%的Cr,使得δ相稳定性增加,进一提高了铁铬锰合金的耐锌腐蚀能力.以锰代镍来制取低成本的铁铬锰耐锌腐蚀合金具有可行性.     

Modelling ductile fracture behaviour from deformation parameters in HSLA steels

In this work, an attempt is made to model the ductile fracture behaviour of two Cu‐strengthened high strength low alloy (HSLA) steels through the understanding of their deformation behaviour. The variations in deformation behaviour are imparted by prior deformation of steels to various predetermined strains. The variations in parameters such as yield strength and true uniform elongation with prior deformation is studied and was found to be analogous to that of initiation fracture toughness determined by independent method. A unique method is used to measure the crack tip deformation characterized by stretch zone depth that also depicted a similar trend. Fracture toughness values derived from the stretch zone depth measurements were found to vary in the same fashion as the experimental values. A semiempirical relationship for obtaining ductile fracture toughness from basic deformation parameters is derived and model is demonstrated to estimate initiation ductile fracture toughness accurately.     

Influence of peritectic phase transformation on hot ductility of high aluminium TRIP steels containing Nb

Abstract

Increasing Al from 0·05 to 1% in Nb containing transformation induced plasticity steel resulted in deepening and considerable widening of the hot ductility trough. Further increase in the Al level to 1·5% produced a trough similar to the low Al steel but having better ductility in the temperature range of 650–800°C. This improved ductility could be ascribed to its finer austenite grain size. Nb(CN) was able to precipitate readily in these steels and was important in influencing the hot ductility of the 0·05 and 1·5%Al steel in the temperature range of 750–1000°C, with ductility improving as the particle size increased with test temperature. No AlN was found in 0·05%Al containing steel, and there was no significant dendritic precipitation of AlN in 1·5%Al containing steel, although precipitation of AlN in plate form was readily observed. In 1%Al steel, copious dendritic precipitation of AlN was present at the γ grain boundaries, leading to rock candy fracture. The poor ductility shown in 1%Al containing steel is due to a combination of this dendritic precipitation, which took place only in a steel of peritectic carbon composition, and its coarse grain size. Both low and 1·5%Al containing steels had compositions outside the peritectic range. It is strongly advised that for this type of steel, the composition should be designed to fall outside the peritectic carbon range.     

Oxidation behavior of ferritic/martensitic steels in flowing supercritical water

The oxidation behavior of two Ferritic/Martensitic(F/M)steels including novel SIMP steel and commercial P91 steel were investigated by exposure to flowing deaerated supercritical water(SCW)at 700℃for up to 1000 h.The kinetic weight gain curves follow parabolic and near-cubic rate equations for SIMP and P91 steels,respectively.X-Ray Diffraction analysis showed the presence of magnetite and a spinel phase in flowing SCW for both steels.The morphology and structure of the oxide scales formed on these two steels were analyzed.The relationship between the microstructure and oxidation behavior and the reason that SIMP steel showed better oxidation resistance than P91 steel were discussed.     

The hot ductility of Nb/V containing high Al,TWIP steels

Abstract

The hot ductility of Nb/V containing high Al, twin induced plasticity (TWIP) steels has been examined over the temperature range 650–1150°C after melting and after ‘solution treatment’. Previous work had shown that the hot ductility is poor for the 1·5 mass-%Al, TWIP steel due to precipitation of AlN at the austenite grain boundaries, the depth of the trough being similar to that for an X65 grade pipeline steel but with the trough covering a much wider temperature range. Adding Nb and V made the ductility even worse due to the additional precipitation of NbCN and VN. Very low reduction of area values, 10–20% were obtained in the temperature range 700–900°C. Increasing the cooling rate to the test temperature resulted in even worse ductility. The ductility of these steels after ‘solution treatment’ is similar to that obtained after melting but when the cast was hot rolled followed by ‘solution treatment’ and cooling to the test temperature ductility improved due to grain refinement.     

Tribological evaluation of high-speed steels with a regulated carbide phase

Wear resistance of a commercial steel and titanium–niobium high-speed steels with a regulated carbide phase was evaluated by employing a micro-scale abrasive wear test with alumina particles. The worn volumes and corresponding wear coefficients were the lowest for the new non-ledeburitic grades containing titanium, then the two niobium grades, the conventional (both wrought and by powder metallurgy) steels exhibited the worse wear resistance. Fractography SEM observations together with energy-dispersive X-ray (EDX) chemical analysis revealed the decisive role of the steels' MC particles in the wear process. These carbides influenced the abrasion by stoppage of the wear scars and/or changing their trajectories. Directional and nondirectional abrasion modes in the steels tested using alumina and carborundum abrasives were found and are discussed.