Microstructural changes in cast martensitic steel after creep at 620°C

Microstructural changes in the cast steel GX12CrMoWVNbN10-1-1 (Fe–0.11 C–0.31 Si–0.89 Mn–9.57 Cr–0.66 Ni–1.01 Mo–1.00 W–0.21 V–0.06 Nb–0.05 Cu–0.05 N in wt %) have been investigated after tests for long-term strength at a temperature of 620°C in the range of stresses of 120–160 MPa. Upon short-term creep (up to 5000 h), the tempered troostite structure and distribution of particles of proeutectoid constituents change insignificantly, except for the precipitation of particles of the Laves phase ～100 nm in size along boundaries of laths, blocks, packets, and initial austenite grains. Upon long-term creep (to 10000 h), the tempered troostite partially transforms into the subgrain structure, which is accompanied by a decrease in the dislocation density from 6.4 × 10¹⁴ to 3.1 × 10¹³ m^–2 and connected with growth of sizes of M₂₃C₆ carbides of 105–150 nm and particles of the Laves phase to 380 nm, due to the dissolution of these particles located along path boundaries. Upon long-term creep, the average size of V(C,N) particles increases from 45 to 64 nm (while Nb(C,N) particles increase from 48 to 87 nm), and the Nb content in V-enriched carbonitrides and the V content in Nb-enriched M(C,N) particles substantially decrease. No formation of the Z phase has been revealed. The combination of M(C,N) nanoparticles with the presence of W in the solid solution has been found to be responsible for the enhanced high-temperature strength of the steel.     

Conversion of MX nitrides to Z-phase in a martensitic 12% Cr steel

A 12% Cr model steel was designed with the purpose of studying the nucleation and growth of modified Z-phase, Cr(V,Nb)N. The model alloy develops Z-phase after relatively short ageing times and contains only nitrides of Cr, V and Nb. Interferences from the presence of carbides and the development of Laves phase were avoided by keeping the C, W and Mo contents as low as possible. Transmission electron microscopy and X-ray diffraction analysis of extracted particles were used to follow the evolutions of phase composition, phase morphology and phase fraction, particularly of the precipitation of Z-phase, during ageing at 600, 650 and 700 °C for up to 10³ h. The development of Z-phase appears to be accomplished by the diffusion of Cr atoms into (V,Nb)N particles and their subsequent conversion into cubic or tetragonal Z-phase. Studies at various temperatures indicate that Z-phase development proceeds fastest at 650 °C and that Z-phase forms faster at prior austenite grain boundaries.     

Toughness recovery of modified 9Cr–1Mo steel weld metals after long-term thermal ageing and its evaluation by electrochemical measurement

Recently, thermal power plants have tended to operate under higher temperature and pressure steam conditions for CO₂ reduction. Modified 9Cr–1Mo steels are used in the ultra-super critical power plant because of their excellent creep properties. However, the toughness of base metal decreases after long-term thermal ageing at operation temperature. Moreover, toughness of weld metal is lowest in the MIG weldment. In this study, metallurgical factors of toughness of the modified 9Cr–1Mo steel weld metals by thermal ageing at operation temperature were investigated. And the evaluation method of toughness by the electrochemical measurement used with 5% sulphuric acid aqueous solution was investigated.

The weld metal that received post-welding heat treatment (PWHT: 1023 K and 5.4 ks) decreased toughness by thermal ageing in 873 K and 31.5 Ms. However, toughness of the welds after thermal ageing was recovered to the same level as PWHT welds when the thermal aged welds received the same thermal history as PWHT. A lot of the large Laves phase was observed in the weld metal after the thermal ageing. However, almost all of the Laves phase dissolved in parent phase by the same thermal history as PWHT. Therefore, it seemed that the decrease and the recovery of toughness were mainly determined by the behaviour of precipitation of the Laves phase. The peak of the current density (Ip) in the electrochemical measurement appeared in the weld metals that precipitated a lot of large Laves phase. It seemed that appearance of Ip was caused by the dissolution of the Laves phase. A good correlation between toughness and Ip was observed. Therefore, it can be said that toughness of the weld metals is supposed to be predicted using an Ip of the electrochemical measurement.     

Effect of stresses on the structural changes in high-chromium steel upon creep

The effect of stresses on the microstructure and dispersed particles in a heating-performance Fe?0.12C–0.06Si–0.04Ni–0.2Mn–9.5Cr–3.2Co–0.45Mo–3.1W–0.2V–0.06Nb–0.005B–0.05N (wt %) steel has been studied under long-term strength tests at Т = 650°C under initial applied stresses ranging from 220 to 100 MPa with a step of 20 MPa. Under an applied stress of 160 MPa, which corresponds to a time to fracture of 1703 h, a transfer from short- to long-term creep takes place. It has been shown that alloying with 3% Co and an increase in W content to 3% significantly increase the short-term creep resistance and slightly increase the long-term strength upon tests by more than 10⁴ h. The transfer from short- to the long-term creep is accompanied by substantial changes in the microstructure of the steel. Under long-term creep, the solid solution became depleted of tungsten and of molybdenum down to the thermodynamically equilibrium content of these elements in the solid solution, which leads to the precipitation of a large amount of fine particles of the Laves phase at the boundaries of laths and prior austenitic grains. At a time to fracture of more than 4 × 10³ h, the coalescence of the M₂₃С₆ carbides and Laves-phase particles occurs, which causes the transformation of the structure of fine tempered martensite lath structure into a subgrained structure.     

Effects of hot compression on carbide precipitation behavior of Ni—20Cr—18W—1Mo superalloy

The effect of hot compression on the grain boundary segregation and precipitation behavior of M₆C carbide in the Ni–20Cr–18W–1Mo superalloy was investigated by thermomechanical simulator, scanning electronic microscope (SEM) and X-ray diffraction (XRD). Results indicate that the amount of M₆C carbides obviously increases in the experimental alloy after hot compression. Composition analyses reveal that secondary M₆C carbides at grain boundaries are highly enriched in tungsten. Meanwhile, the secondary carbide size of compressive samples is 3–5 μm in 10% deformation degree, while the carbide size of undeformed specimens is less than 1 μm under aging treatment at 900 and 1000 °C. According to the thermodynamic calculation results, the Gibbs free energy of γ-matrix and carbides decreases with increase of the compression temperature, and the W-rich M₆C carbide is more stable than Cr-rich M₂₃C₆. Compared with the experimental results, it is found that compressive stress accelerates the W segregation rate in grain boundary region, and further rises the rapid growth of W-rich M₆C as compared with the undeformed one.     

Laves phase fields in Cr–Zr–Nb and Cr–Zr–Hf alloy systems

The phase fields of the Laves phase in the Cr–Zr–Nb and Cr–Zr–Hf alloy systems were investigated at 1573 K. The Laves phase formed in the Cr–Zr–Nb alloy system had a broad off-stoichiometric range in the center of ZrCr₂–NbCr₂ pseudo-binary line, while the Laves phase formed in the Cr–Zr–Hf alloy system had a uniform and limited off-stoichiometric range along ZrCr₂–HfCr₂ pseudo-binary line. The results are discussed, in terms of geometric concept of atomic sizes of the constituent atoms.     

Effect of Grain Size on the Precipitation Behaviour in Super-Ferritic Stainless Steels During a Long-Term Ageing

A 27.6Cr-3.6Mo-2Ni alloy was solution treated and then aged for a long time to study the effect of grain size on precipitation behaviour by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The experimental results demonstrated that the average grain size increased from 46.3 ± 6.2 to 101.8 ± 13.5 μm and the grain boundary length per unit area decreased from 3.3 × 10~4 to 1.7 × 10~4 m/m~2 with an increasing annealing temperature from 1100 to 1200 ℃. After ageing at 800 ℃, the σ-phase,χ-phase and Laves phase were observed. As the ageing time increased, the σ-phase notably increased, while the χ-phase and Laves phase gradually decreased before finally vanishing after ageing for 400 h. The σ-phase precipitation kinetics curves consisted of two parts, and the grain size had a significant effect on the first stage of the precipitation curves due to the abundance of nucleation sites in the specimens with finer grains. The Laves phase was transformed from Nb(C,N) particles by Nb diffusion. As the ageing time increased, the ferrite phase decreased due to the transformation of the ferrite phase to the σ-phase, and then C was expelled into the untransformed ferrite grains. Moreover, new Nb(C,N) particles were formed by Nb diffusion from the Laves phase, resulting in the absence of the Laves phase.     

含Nb元素堆焊层金属中碳化物的析出行为

以堆焊连铸辊为研究对象,研制三种不同合金元素Nb加入量的药芯焊丝,采用金相显微镜和扫描电镜对其显微组织、碳化物形貌进行了观察. 采用X射线衍射仪对其相结构进行了测定. 采用Thermo-Calc软件对含铌堆焊层金属中碳化物的析出行为进行分析. 结果表明,堆焊层金属显微组织为铁素体、M₂₃C₆和MC. 随着Nb元素含量增加,其显微组织得到细化,NbC沿晶界析出. 热力学计算结果表明,析出碳化物主要为MC,M₂₃C₆. 随着Nb元素含量的增加,MC析出量增多,M₂₃C₆析出量减小. MC中主要是Nb元素,并溶解了一定量的Mo,V,Cr和Fe元素;M₂₃C₆中主要是Fe,Cr元素,即Nb元素含量变化主要影响MC型碳化物.     

Investigations on the growth kinetics of Laves phase precipitates in 12% Cr creep-resistant steels: Experimental and DICTRA calculations

The growth kinetics of Laves phase precipitates (type Fe₂W) in the early stage of creep (650 °C for 10,000 h) in two 12% Cr ferrite–martensitic steels has been investigated. In one alloy the Laves phase formed on tempering, while in the second alloy the Laves phase precipitated during creep. Kinetic simulations were performed using the software DICTRA. The particle size of the Laves phase was measured on transmission electron microscopy samples. The equilibrium phase fraction of the Laves phase was reached in the first thousand hours. Simulations of particle growth showed good agreement with the experimental results. Competitive growth between M₂₃C₆ and the Laves phase showed that M₂₃C₆ carbides reached their equilibrium after 12 days, whereas the Laves phase reached equilibrium after 3 months. Simulations of the influence of the interfacial energy and addition of Co, Cu and Si on Laves phase precipitation are presented.     

Improving Corrosion Resistance of Ferrous Alloy to Molten Zn by Modifying the Laves Phase Characteristics

The Laves phase morphology in the Fe25Mo14Cr10Ni1Si (wt.%) alloy was modified by Si addition to improve the corrosion resistance of the ferrous alloy to molten zinc. The Si-containing alloy showed a woven, needle-like Laves phase with higher Mo content than that of the Fe25Mo14Cr10Ni alloy. Corrosion resistance to molten Zn for the Si-containing alloy was more than 20 times higher than that of the silicon-free alloy mainly as a result of the characteristics of the modified Laves phase. This phase was oriented perpendicular to the Zn-diffusion direction, which effectively prevented corrosion by the molten Zn, leading to a denser FeZn₁₃ layer rather than the FeZn₁₀ layer produced in the Fe25Mo14Cr10Ni alloy.     

Ageing behavior study of 5Cr–0.5Mo steel by magnetic Barkhausen emissions and magnetic hysteresis loop techniques

Magnetic hysteresis loop and Barkhausen emissions were recorded and analysed for 5Cr–0.5Mo steel after ageing at 600 °C for various lengths of time. At the initial stage of ageing the interstitial carbon diffuses towards the grain boundary making the matrix magnetically softer. During this stage, extending up to 200 h of ageing, magnetic softness was found to be increasing. This was associated with a decrease in coercivity and increase in Barkhausen voltage. Beyond 200 h of ageing the precipitation of alloy carbides attain subsequent growth, making the material magnetically harder. The evolution of carbides was studied using SEM-EDAX analysis. It was observed that most of the carbides transformed into M₂₃C₆ type after ageing for 400 h.     

Pulverization mechanism of the multiphase Ti–V-based hydrogen storage electrode alloy during charge/discharge cycling

Pulverization is an important key factor for the electrochemical cycle stability of many hydrogen storage alloys. In this paper, the pulverization mechanism of the multiphase Ti–V-based hydrogen storage alloy which mainly consists of a V-based solid solution phase with the BCC structure and a C14 Laves phase is studied based on a sample material of the Ti_0.8Zr_0.2V_2.7Mn_0.5Cr_0.6Ni_1.25Fe_0.2 alloy. The microstructure of the alloy and the morphology change of the alloy electrode during the charge/discharge process were observed by transmission electron microscope, scanning electron microscope and atomic force microscope, etc. The effect of mechanical properties of the V-based phase and the C14 Laves phase on the pulverization behavior of the Ti–V-based alloy is discussed. The results show that microcracks initially occur at the phase boundary of the V-based phase and the C14 Laves phase and then extend to the C14 Laves phase in the charge/discharge process. The phase boundary is composed of a Ti segregated amorphous layer with a thickness of about 90 nm, mismatching with the crystallized V-base phase and C14 Laves phase. The toughness of the C14 Laves phase is much lower and the hardness is higher than that of the V-based phase. The weak bonding strength of the phase boundary, the lower toughness of the C14 Laves phase and the large volume expansion/contraction of the C14 Laves phase during charge/discharge cycling are the main factors that cause the pulverization of the Ti–V-based alloy.     

Structure and properties of titanium-free maraging alloys

The changes in the structure, phase composition, and physicomechanical properties of titanium-free maraging alloys based on the Fe-15–23% Ni-(Co, Mo, V) system after heating to the single-phase α field and two-phase α + γ field have been studied. It has been established that the strengthening of N15K10M5F5-type maraging alloys is caused by the precipitation of fine particles (20–50 nm) of intermetallic phases such as the fcc Ni₃(Mo, V) phase and the Fe₂(Mo, V) Laves phase (in the N23K9M6 alloys, with the formation of the Ni₃Mo and Fe₂Mo phases). It has been shown that the two-step aging of the N15K10M5F5 alloy leads to an additional strengthening by 200–250 MPa and provides the achievement of the ultimate tensile strength σ_u=2400?2500 MPa. The high-strength N15K10M5F5 maraging alloys are obtained with two levels of the coercive force H _c: (a) semihard maraging alloys with H _c=20?50 Oe and σ_u=2100?2400 MPa; and (b) hard magnetic maraging alloys with H _c=180?230 Oe and σ_u=1500?1800 MPa. The high-strength titanium-free N15K10M5F5 and N23K9M6 maraging alloys possess many properties characteristic of structural, elastic, and magnetic alloys and are thus multifunctional materials. These alloys can be used for advanced high-tech articles and as high-strength magnetic materials.     

Influence of strain on precipitation reactions during creep of an advanced 9% chromium steel

Creep tested samples of the 9% chromium steel P92 were investigated using energy filtered transmission electron microscopy (EFTEM) and atom probe field ion microscopy (APFIM). The mean size and the volume fraction of precipitates of type M₂₃C₆, VN and Laves phase as a function of creep time and temperature were determined. A comparison with isothermally aged material showed that coarsening of M₂₃C₆ carbides is accelerated by the strain, while the effect of strain on VN precipitates is insignificant. It was also found that the number density of Laves phase particles is higher in creep tested material compared to isothermally aged material. Possible mechanisms to explain these observations are discussed.     

Crystallography and structural evolution during reverse transformation in an Fe–17Cr–0.5C tempered martensite

The mechanism and the crystallography of austenite and δ-ferrite formation from tempered martensite at temperatures of 900–1200°C have been studied by means of transmission electron microscopy in an Fe–17Cr–0.55C alloy. It was found that austenite nucleates within ferrite at low angle, high angle and twin-related lath boundaries as well as at high angle equiaxed grain boundaries in contact with M₂₃C₆ grain/lath boundary carbides. The austenite grains are in a cube–cube relationship with the M₂₃C₆ carbide particles and bear the Kurdjumov–Sachs orientation relationship with at least one of the adjacent ferrite grains. They are often in the Kurdjumov–Sachs relationship with both ferrite laths separated by a high angle boundary as far as the laths had formed from the same austenite. The {111}_A close packed plane of γ precipitate is parallel to the {110}_F plane most parallel to the grain boundary. The close packed planes of some austenite grains nucleating at the high angle lath boundaries are parallel to the close packed planes of both ferrite laths. These crystallographic features often result in a single variant of austenite orientation at a grain boundary. After nucleation, the austenite grains grow by the migration of both semicoherent and incoherent interfaces. These results demonstrate that a specific orientation relationship is preferred for the austenite nucleation, but is not necessary for the subsequent growth. The kinetics of austenite growth are controlled by chromium diffusion. The δ-ferrite particles precipitate at high temperatures as a non-equilibrium phase. No rational orientation relationship between δ-ferrite and retained austenite was found. The experimental results are discussed qualitatively in terms of the thermodynamic predictions using the software ThermoCalc, assuming local equilibrium at the moving interfaces.     

Static Recrystallization of Cold Rolled Intermetallic Fe17Al4Cr0.3Zr Alloy

The final microstructure of cold rolled intermetallic disordered alloy Fe17Al4Cr0.3Zr was rebuilt during the annealing at moderate temperatures in the range of 800 to 900?°C. The time necessary to obtain recrystallized structure was determined at several annealing temperatures to optimize the processing technology of the plates. The phases present in the material during this process were identified. The grain growth (grain boundary movement) during static recrystallization (SRX) is connected with the interaction with an array of the Laves phase ??₁(Fe,Al)₂Zr and ZrC particles. The Avrami-based phenomenological model describing kinetics of SRX was developed. The activation energy for recrystallization was estimated.     

Microstructural evolution in a strip-cast Ni-base superalloy

Microstructure and mechanical properties of the strip-cast Ni-base superalloy(Hastelloy-X) alloy have been compared with those of a conventionally ingot-cast alloy. As-cast strip shows a fine columnar dendritic structure as a result of a relatively high cooling rate of 10² -10⁴ K/sec during the process. The alloying elements, such as Cr and Fe, are homogeneously distributed in the γ matrix of the as-cast strip. Whereas, Mo is segregated at the center part of the as-cast strip. Mo distribution, however, becomes homogeneous after cold rolling and subsequent heat treatment at 1175°C. Two types of carbide, a Mo-rich M₆C type and a Cr-rich M₂₃C₆ type, are present in the γ matrix of the as-cast and rolled strips. Rolling and subsequent heat treatment of the strip-cast alloy results in a fine grain structure compared to the ingot-cast alloy. The γ matrix grains in stripcast and ingot-cast alloy are approximately 14 μm and 34 μm in diameter respectively. Superior tensile properties in the strip-cast alloy is due to the fine microstructural evolution during the process.     

Characterization of microstructure of HAZs in as-welded and service condition of P91 pipe weldments

Steels 9-12% Cr, having the high creep rupture strength are advocated for the modern low polluting thermal power plants. In the present investigation, the P91 pipe weldments have been characterized for microstructural responses in as-welded, post-weld heat treatment (PWHT) and ageing conditions. The PWHT of welded samples were carried out at 760 °C for time of 2 h and ageing at 760 °C for 720 h and 1440 h, respectively. The effect of time has been studied on precipitates size, distribution of precipitates and grain sizes present in various zones of P91 steel weldments. The impact toughness and hardness variation of heat affected zone (HAZ) have also been studied in as-welded condition as well as at different heat treatment condition. A significant change was observed in grain size and precipitates size after each heat treatment condition. The maximum impact toughness of HAZ was obtained after PWHT at 760 °C for 2 h. The main phase observed in weld fusion zone in as-welded, PWHT and ageing conditions were M₂₃C₆, MX, M₇C₃, Fe-rich M₃C and M₂C. The unwanted Z-phase (NbCrN) was also noticed in weld fusion zone after ageing of 1440 h.