Accurate determination of the number density of G-phase precipitates in thermally aged duplex stainless steel

G-phase precipitation in the ferrite phase in thermally aged duplex stainless steel (DSS) was investigated. A needle-shaped sample of DSS aged at 673?K for 5000?h was observed by transmission electron microscopy (TEM), and subsequently by atom probe tomography (APT). The precipitates of the G-phase observed by TEM corresponded well to clustering atoms observed by APT. On the other hand, regarding the precipitates of the G-phase that formed in an earlier stage of aging, the present study suggests that not all the precipitates can be detected by TEM. A large area of DSS aged at 673?K for 5000?h containing both the ferrite and austenite phases was observed. The number density of precipitates of the G-phase in the ferrite phase was small in the vicinity of the phase boundary and increased with the distance between the phase boundary and each field of view. The number density reached an almost constant value at a distance of approximately 4?µm from the phase boundary. The suppression of G-phase precipitation in the vicinity of the phase boundary is discussed in terms of the depletion of alloying elements that comprise the G-phase.     

Effects of aging temperature on G-phase precipitation and ferrite-phase decomposition in duplex stainless steel

G-phase precipitation and ferrite-phase decomposition in a cast duplex stainless steel (DSS) aged at 623–723?K for up to 8000?h were investigated using atom probe tomography (APT). Large sample volume was observed in every APT experiment, which yielded significantly statistical results. The number density of G-phase precipitates tended to be high and their sizes were small at lower aging temperatures. G-phase precipitates grew during prolonged isothermal aging. The concentrations of nickel, silicon, manganese and molybdenum in G-phase precipitates tended to increase as the precipitates grew. Heterogeneous distributions of alloying elements within G-phase precipitates were observed. An interesting positional relationship of G-phase precipitates with dislocations was revealed. Regarding the ferrite-phase decomposition, local chromium concentrations in the ferrite phase varied fast at higher aging temperatures. Good correlation between the variation of local chromium concentrations and aging conditions was revealed, which indicates that the variation can be estimated for arbitrary aging conditions. Representative distances between chromium-enriched and chromium-diluted regions were long at higher aging temperatures. Time exponent of the representative distances of ferrite-phase decomposition as well as the size of G-phase precipitates increased with aging temperatures.     

A Mössbauer spectrometry study on the phase decomposition of cast duplex stainless steel

Cast CF3M duplex stainless steel having 25% of ferrite in volume fraction was aged at 723 K for time periods up to 10000 h. Phase decomposition of ferrite was investigated by Mössbauer spectroscopy. Ferrite decomposed initially via a spinodal process to finally yield the Fe-rich and the Cr-rich phase. The hyperfine magnetic field distribution obtained from the experimental Mössbauer spectrum was analyzed by assuming trinomial distribution of main constituent atoms Fe, Cr, Ni to determine Cr and Ni content of the Fe-rich phase. Main compositions of the phase were 84 at.% Fe, 11 at.% Cr, 5 at.% Ni.     

Structure and Phase Content of a Weld in Fe–0.09C–2Mn–1Si Steel

The structure and phase content of a weld in Fe–0.09C–2Mn–1Si steel are investigated by the methods of transmission electron microscopy (TEM) and metallography. A gradient weld structure is established. The manner in which the phase content of steel, the ferrite and pearlite grain sizes, and the morphology of cementite particles depend on the increasing distance from the weld center is elucidated.     

Structural characterization and magnetic properties of superparamagnetic zinc ferrite nanoparticles synthesized by the coprecipitation method

Single phase zinc ferrite (ZnFe₂O₄) nanoparticles have been prepared by the coprecipitation method without any subsequent calcination. The effects of precipitation temperature in the range 20–80 °C on the structural and the magnetic properties of zinc ferrite nanoparticles were investigated. The crystallite size, microstructure and magnetic properties of the prepared nanoparticles were studied using X-ray diffraction (XRD), Fourier transmission infrared spectrum, transmission electron microscope (TEM), energy dispersive X-ray spectrometer and vibrating sample magnetometer. The XRD results showed that the coprecipitated nanoparticles were single phase zinc ferrite with mixture of normal and inverse spinel structures. Furthermore, ZnFe₂O₄ nanoparticles have the crystallite size in the range 5–10 nm, as confirmed by TEM. The magnetic measurements exhibited that the zinc ferrite nanoparticles synthesized at 40 °C were superparamagnetic with the maximum magnetization of 7.3 emu/g at 10 kOe.     

Laves Phases in Ferrite-Martensite EC-181 Steel

The microstructure and phase composition of EC-181 ferrite-martensite steel were studied in dependence on their heat treatment (temperature and aging time after quenching from 1080°C). It was established that Laves phases are formed only at the boundaries of ferrite grains, whereas Me ₂₃C₆ and V₂C carbides are formed in the ferrite and martensite components of the structure.     

High resolution electron microscopy of precipitates in high Co-Ni alloy steel

In the secondary hardening reaction in ultrahigh strength steel of high Co-Ni alloy, the needle-shaped precipitating carbide is the main strengthening phase. Particular attention has been paid to the nucleation, growth and coarsening of the precipitate and its interface with the ferrite matrix. High resolution transmission electron microscopy observations show that when tempered at a low temperature condition of 454 degrees C for 5h, the precipitating carbides begin to nucleate in the form of clusters; at peak hardening tempered at 482 degrees C, the growing carbides are fully coherent with the matrix, exhibit black-white contrast in bright-field images and have their own hexagonal crystalline structure as M(2)C. Coarsening carbides tempered at high temperature lost their coherence and exhibited Moiré fringes. Lattice images directly indicate the crystallographic relationship of M(2)C carbides and ferrite, [100](alpha)//[1101](beta), [100](alpha)//[1120](beta).     

Formation of fully pearlitic microstructure in medium carbon steel

Pearlitic microstructure can be obtained when austenite of eutectoid composition is slowly cooled from high temperature to below the Ae₃ temperature. It is also possible to induce such structure in hypo-eutectoid composition of austenite through proper heat treatment as well. However, in the current work, one hypo-eutectoid steel during very slow cooling only produced completely pearlitic microstructure which was not expected from a steel with such composition. The calculations carried out considering orthoequilibrium condition actually predicted the presence of about 37% ferrite in the microstructure. Further calculations considering different equilibrium modes and kinetics of transformation indicates that the composition and thermal condition of the steel under consideration was such that proeutectoid ferrite formation could not start before the composition reaches to the Negligible Partitioning Local Equilibrium phase boundary which further coincides with the area described by Hultgren extrapolation and thus, the steel completely transforms to pearlite even with hypo-eutectoid composition during very slow cooling.     

X-ray diffraction and Mössbauer spectroscopy studies of cementite dissolution in cold-drawn pearlitic steel

Cementite dissolution in cold-drawn pearlitic steel (0.8 wt.% carbon) wires has been studied by quantitative X-ray diffraction (XRD) and Mössbauer spectroscopy up to drawing strain 1.4. Quantification of cementite-phase fraction by Rietveld analysis has confirmed more than 50% dissolution of cementite phase at drawing strain 1.4. It is found that the lattice parameter of the ferrite phase determined by Rietveld refinement procedure remains nearly unchanged even after cementite dissolution. This confirms that the carbon atoms released after cementite dissolution do not dissolve in the ferrite lattice as Fe-C interstitial solid solution. Detailed analysis of broadening of XRD line profiles for the ferrite phase shows high density of dislocations (～10¹⁵/m²) in the ferrite matrix at drawing strain 1.4. The results suggest a dominant role of ?1?1?1? screw dislocations in the cementite dissolution process. Post-deformation heat treatment leads to partial annihilation of dislocations and restoration of cementite phase. Based on these experimental observations, further supplemented by TEM studies, we have suggested an alternative thermodynamic mechanism of the dissolution process.     

Quasi in situ Ni K‐edge EXAFS investigation of the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant

Ni species on the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant were studied by Ni K‐edge EXAFS and TEM measurement without contact of the catalysts with air. The Ni–Mo coordination shell related to the Ni–Mo–S phase was observed in the spent catalyst by quasi in situ Ni K‐edge EXAFS measurement with a newly constructed high‐pressure chamber. The coordination number of this shell was almost identical to that obtained by in situ Ni K‐edge EXAFS measurement of the fresh catalyst sulfided at 1.1 MPa. On the other hand, large agglomerates of Ni₃S₂ were observed only in the spent catalyst by quasi in situ TEM/EDX measurement. MoS₂‐like slabs were sintered slightly on the spent catalyst, where they were destacked to form monolayer slabs. These results suggest that the Ni–Mo–S phase is preserved on the spent catalyst and Ni₃S₂ agglomerates are formed by sintering of Ni₃S₂ species originally present on the fresh catalyst.     

Orientation relationship in Eurofer martensitic steels

Both TEM and SEM/EBSD orientation measurements are carried out on a Eurofer97 martensitic steel. The influence of the prior austenitic grain size is studied using dedicated heat treatments. The intra laths misorientation is estimated by TEM. SEM/EBSD orientation mapping enable to study the actual orientation relationship (OR) between the parent austenitic phase and the martensitic phase. Neither the Nishiyama–Wasserman nor the Kurdjumov–Sachs OR is able to account for both the misorientation angle distributions, the pole figure and the misorientation axes measured. The mixed OR recently proposed by Gourgues et al. (Electron backscattering diffraction study of acicular ferrite, bainite, and martensite steel microstructures, Mater. Sci. Tech. 16 (2000), pp. 26–40.) and Sonderegger et al. (Martensite laths in creep resistant martensitic 9–12%Cr steels – Calculation and measurement of misorientations, Mater. Characterization (2006), in Press.) seems to be able to account for most of these results. Based on this OR, a new angular criterion is proposed to detect blocks of laths.     

Studies of structure and morphology of sputter-deposited stainless steel–nitrogen films

Stainless steel films doped with nitrogen were deposited on heated and unheated (100) silicon substrates by radio-frequency magnetron sputtering of an austenitic stainless steel target in argon and nitrogen gas mixtures, containing a range of nitrogen compositions. The evolution of phases, morphologies and grain structures in the resultant films was studied by X-ray diffraction and field emission scanning electron microscopy. It was found that, with increasing nitrogen composition in the gas mixture, the crystalline structure of the films deposited on the heated substrates changed from bcc ferrite (α), to nitrogen-stabilized fcc austenite (γ), then to distorted expanded austenite phase (γ_N) with nitrogen supersaturation, and finally to the newly discovered fcc ‘MN’ phase with ideal cubic symmetry and further enlarged lattice. On the unheated substrates, the phase-evolution trend was found to be different for % N₂ above 10. For the 25% N₂ film, amorphous phase formed along with the crystalline austenite and ferrite phases, while the percentage of amorphous content decreased when % N₂ was increased to 50. This different trend was understood to be due to the role of increase in % N₂ in decreasing the energy loss of sputtered species through collisions. The dependence of crystalline phase formation on the energy of sputtered species is less severe on the heated substrates. Although all the films deposited experienced three-dimensional fibrous growths, they exhibited different surface morphology and grain structure. There exists a correlation between film morphology and phase constituents, while grain size was influenced by the nucleation density and the energy and mobility of adatoms that are reduced due to nitrogen incorporation. PACS 68.55.-a; 81.15.Cd     

One-pot production of copper ferrite nanoparticles using a chemical method

Copper ferrite nanoparticles were synthesized via the oxidation of precipitates obtained from the reaction of FeCl₂, CuSO₄ and N₂H₄ in the presence of gelatin. These copper ferrite particles were subsequently examined using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Mössbauer spectroscopy. The average size of the copper ferrite nanoparticles was less than 5 nm, and they exhibited superparamagnetic behavior as a result of their small size. The low temperature Mössbauer spectrum exhibited three sets of sextets, two corresponding to the tetrahedral and octahedral sites of the copper spinel structure and one with small hyperfine magnetic field corresponding to the surface or defects of the nanoparticles. When the ratio of copper salt was increased, the tetrahedral site became preferable for copper, and metallic copper and copper ferrite were both present in a single nanoparticle.     

X-ray diffraction and Mössbauer studies of X20Cr13 steel subjected to ball milling

The powders of X20Cr13 steel were subjected to ball milling process in a planetary ball mill. X-ray diffraction and Mössbauer spectroscopy studies revealed the refinement of the structure of this steel down to a nanocrystalline range practically without any phase transformations. Both techniques allowed to detect the alloyed ferrite as well as residual content of iron containing M₂₃C₆-type carbide, which was dissolved into the ferrite during milling. Hyperfine magnetic fields in ball milled steel samples did not differ significantly from those for the bulk steel disc.     

Quantitative analysis of a complex metal carbide formed during furnace cooling of cast duplex stainless steel using EELS and EDS in the TEM

In this work, a method to determine the atomic ratio of Mo and C within complex metal carbides using EELS in the TEM has been developed. The method is based on the determination of k-factors for given experimental conditions from the EEL spectra of Mo₂C and MoO₃ standards, which had been independently checked by XRD and EPMA. Factors affecting the k_Mo/C value of the Mo₂C standard were also investigated and the value was shown to be insensitive to background subtraction window width but sensitive to prolonged irradiation and specimen thicknesses above a critical value. The method and k-factor obtained from the Mo₂C standard was applied to spectra from a complex metal carbide precipitate formed during furnace cooling of a cast duplex stainless steel. Using EELS and EDS in the TEM, the composition was estimated to be (Cr_1.52Fe_2.33Mo_1.25Ni_0.17Si_0.46)C, which is close to M₆C stoichiometry, and the structure was confirmed by electron diffraction.     

Effect of the grain size on the formation of a nanophase structure and tribological properties of the friction surface of a ceramic made of partly stabilized zirconia

It is found that the wear of the ZrO₂ + 3 mol% Y₂O₃ ceramics with a grain size of 180 nm in the case of dry friction on steel is smaller by a factor of 20–60 than the wear of a ceramic with an average grain size of 700 nm. It is shown that this is due to the fact that a nanophase structure formed on the friction surface of the ceramic with a grain size of 180 nm consists of ferroelastic nanodomains of the nontransformable T′ phase.     

In situ observation of Ni–Mo–S phase formed on NiMo/Al2O3 catalyst sulfided at high pressure by means of Ni and Mo K‐edge EXAFS spectroscopy

To obtain direct evidence of the formation of the Ni–Mo–S phase on NiMo/Al₂O₃ catalysts under high‐pressure hydrodesulfurization conditions, a high‐pressure EXAFS chamber has been constructed and used to investigate the coordination structure of Ni and Mo species on the catalysts sulfided at high pressure. The high‐pressure chamber was designed to have a low dead volume and was equipped with polybenzimidazole X‐ray windows. Ni K‐edge k³χ(k) spectra with high signal‐to‐noise ratio were obtained using this high‐pressure chamber for the NiMo/Al₂O₃ catalyst sulfided at 613 K and 1.1 MPa over a wide k range (39.5–146 nm^?1). The formation of Ni–Mo and Mo–Ni coordination shells was successfully proved by Ni and Mo K‐edge EXAFS measurement using this chamber. Interatomic distances of these coordination shells were almost identical to those calculated from Ni K‐edge EXAFS of NiMo/C catalysts sulfided at atmospheric pressure. These results support the hypothesis that the Ni–Mo–S phase is formed on the Al₂O₃‐supported NiMo catalyst sulfided under high‐pressure hydrodesulfurization conditions.     

Correlative microscopy of a carbide-free bainitic steel

In this work a carbide-free bainitic steel was examined by a novel correlative microscopy approach using transmission Kikuchi diffraction (TKD) and transmission electron microscopy (TEM). The individual microstructural constituents could be identified by TKD based on their different crystal structure for bainitic ferrite and retained austenite and by image quality for the martensite–austenite (M–A) constituent. Subsequently, the same area was investigated in the TEM and a good match of these two techniques regarding the identification of the area position and crystal orientation could be proven. Additionally, the M–A constituent was examined in the TEM for the first time after preceded unambiguous identification using a correlative microscopy approach. The selected area diffraction pattern showed satellites around the main reflexes which might indicate a structural modulation.     

Direct observation of Cu interphase precipitation in continuous cooling transformation by atom probe tomography

Atom probe tomography (APT) combined with electron back scatter diffraction and transmission electronic microscopy (TEM) is utilized to characterize the nature of copper precipitation during austenite–ferrite transformation in a continuous cooling high-strength low-alloy steel. The copper precipitation manners in association with the austenite decomposition kinetics are studied. The prevailing microstructure of the continuous cooling steel consists of acicular ferrite (AF), which is formed at an intermediate cooling rate of 10?°C/s. Besides, a limited volume of polygonal ferrite (PF) because of fast cooling rate and a trace of retained austenite are detected. Numerous copper-rich phase is found by TEM observation both in highly dislocated AF and dislocation-free PF. Generally, the copper-rich precipitates have comparatively large sizes and are considered to be formed by interphase precipitation during austenite–ferrite transformation. A high number density of nanometre sized copper-rich clusters that are lack of diffraction contrast in conventional TEM observation are detected by APT. These smaller copper-rich clusters, which are usually located between the linear-arranged copper-rich precipitates, are considered to be formed from supersaturated solid solution after the cessation of austenite–ferrite transformation. That means an ageing reaction for Cu precipitation occurs during continuous cooling transformation. The copper-rich precipitates and clusters are both rich in nickel, manganese and iron.     

The effect of chloride ions on the corroded surface layer of 00Cr22Ni5Mo3N duplex stainless steel under cavitation

The effects of Cl⁻ on the corroded surface layer of 00Cr22Ni5Mo3N duplex stainless steel under cavitation in chloride solutions were investigated using nanoindentation in conjunction with XRD and XPS. The results demonstrate that Cl⁻ had a strong effect on the nano-mechanical properties of the corroded surface layer under cavitation, and there was a threshold Cl⁻ concentration. Furthermore, a close relationship between the nano-mechanical properties and the cavitation corrosion resistance of 00Cr22Ni5Mo3N duplex stainless steel was observed. The degradation of the nano-mechanical properties of the corroded surface layer was accelerated by the synergistic effect between cavitation erosion and corrosion. A key factor was the adsorption of Cl⁻, which caused a preferential dissolution of the ferrous oxides in the passive film layer on the corroded surface layer. Cavitation further promoted the preferential dissolution of the ferrous oxides in the passive film layer. Simultaneously, cavitation accelerated the erosion of the ferrite in the corroded surface layer, resulting in the degradation of the nano-mechanical properties of the corroded surface layer on 00Cr22Ni5Mo3N duplex stainless steel under cavitation.