Influence of carbon content on microstructure and tempering behaviour of 2 1/4 Cr 1 Mo steel

Transmission electron microscopic studies aimed at elucidating the effect of carbon level on the tempering behaviour of 2 1/4 Cr 1 Mo steels have been carried out. Specimens with two different carbon levels (0.06% and 0.11 %) were cooled in flowing argon gas (AC) from an austenitization temperature of 1323 K and tempered at 823, 923 and 1023 K for times ranging from 2 to 50 h. The tempering behaviour at these temperatures for the two carbon levels is found to differ in the nature of secondary hardening at lower temperatures, variation in the time to peak hardness and the saturation level of hardness at long tempering times. Based on a detailed study, using analytical electron microscopy, on the morphology, crystallography and microchemistry of secondary phases, the factors governing the observed variations in tempering behaviour are related to the difference in the dissolution rate of bainite, nucleation of acicular M₂C carbides and transformation rate of primary carbides into secondary alloy carbides. The carbides which promote softening were identified as M₇C₃, M₂₃C₆ and M₆C, whereas hardening is mainly imparted by M₂C.     

Microstructural characteristics of gas tungsten arc synthesised Fe-Cr-Si-C coating

Abstract

The gas tungsten arc (GTA) method was used to synthesise Fe-Cr-Si-C alloy coatings, and processing effects on the coating were investigated experimentally. Coatings were developed on an AISI type 1040 steel substrate. Four different regions were obtained in the surface coating; and in these regions either a hypoeutectic or a hypereutectic microstructure was found. The hypoeutectic microstructure consisted of primary dendrites of austenite (γ) phase and eutectic M₇C₃ (M=Cr,Fe) carbides. On the other hand, the hypereutectic microstructure consisted of M₇C₃ primary carbides and eutectic. A hypoeutectic or hypereutectic microstructure was determined by the combination of particularly carbon concentration, solidification rate, and extent of substrate melting. The higher hardness of the hypereutectic microstructure is attributed especially to the formation of M₇C₃ primary carbides. The lower hardness of the hypoeutectic microstructure is related to three effective parameters: first, the presence of γ phase in the primary dendrites; second, excessive dilution from the base material; and third, relatively low concentrations of chromium and carbon.     

Laser in-situ synthesis of mixed carbide coating on steel

A 2.5 KW Nd:YAG laser was employed to modify the surface of a AISI 1010 steel deposited with a precursor powder mixture of Fe, Ti, Cr and C. In-situ formation of TiC and chromium carbides [M₇C₃ (M = Fe, Cr) and Cr₇C₃] was observed as function of laser processing power at constant scan speed. Although TiC was present in all the samples, the chromium carbides were absent in samples processed at certain laser powers. Corresponding to this behavior, variation in mechanical properties of the coating was observed. The hardness and wear properties of the samples without chromium carbides was inferior in comparison to samples with both TiC and chromium carbides.     

Effect of carbon content on microstructure and corrosion behavior of hypereutectic Fe–Cr–C claddings

The aim of this study was to examine the influence of carbon content on the microstructures and corrosion characteristics. The results showed that the hypereutectic microstructure comprised primary (Cr,Fe)₇C₃ carbides and the eutectic colonies [γ-Fe + (Cr,Fe)₇C₃]. The amounts of primary (Cr,Fe)₇C₃ carbides increased from 33.81 to 86.14% when carbon content increased from 3.73 to 4.85 wt%. The corrosion resistance of the hypereutectic alloy with 4.85 wt% C was about 20 times higher than that with 3.73 wt% C. The galvanic corrosion occurred in all claddings due to difference of corrosion potential between primary carbide and austenite. The dense distribution of primary carbides could retard the austenitic matrix from selective corrosion. The austenite dissolved the Fe²⁺ ions and formed a Cr₂O₃ film under 3.5% NaCl aqueous solution.     

Carbide transformation in carburised zone of 25Cr35NiNb+MA alloy after high-temperature service

Microstructure evolution due to carburising of a 25Cr35NiNb+MA ethylene pyrolysis furnace tube was investigated after service for approximately 4 years. The microstructure of 25Cr35NiNb+MA alloy was examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) equipped with energy-dispersive X-ray spectroscopy and high-resolution transmission electron microscopy (TEM). The results revealed that M₂₃C₆ carbides of the 25Cr35NiNb+MA alloy had coarsened and transformed to M₇C₃ carbides with a heavily faulted structure during carburising. The content of M₇C₃ carbide increased closer to the inner wall. A large number of dislocations had been observed surrounding the carbides and some formed dislocation walls. The carbide transformation mechanism and the effect of the dislocation walls are discussed.     

Effect of carbon content on solidification behaviors and morphological characteristics of the constituent phases in Cr-Fe-C alloys

A combination of transmission electron microscopy, electron backscatter diffraction and wavelength dispersive spectrum has been used to identify crystal structure, grain boundary characteristic and chemical composition of the constituent phases in Cr-Fe-C alloys with three different carbon concentrations. Depending on the three different carbon concentrations, the solidification structures are found to consist of primary α-phase and [α + (Cr,Fe)₂₃ C₆] eutectic in Cr-18.4Fe-2.3 C alloy; primary (Cr,Fe)₂₃ C₆ and [α + (Cr,Fe)₂₃ C₆] eutectic in Cr-24.5Fe-3.8 C alloy and primary (Cr,Fe)₇ C₃ and [α + (Cr,Fe)₇ C₃] eutectic in Cr-21.1Fe-5.9 C alloy, respectively. The grain boundary analysis is useful to understand growth mechanism of the primary phase. The morphologies of primary (Cr,Fe)₂₃ C₆ and (Cr,Fe)₇ C₃ carbides are faceted structures with polygonal shapes, different from primary α-phase with dendritic shape. The primary (Cr,Fe)₂₃ C₆ and (Cr,Fe)₇ C₃ carbides with strong texture exist a single crystal structure and contain a slight low angle boundary, resulting in the polygonal growth mechanism. Nevertheless, the primary α-phase with relative random orientation exhibits a polycrystalline structure and comprises a massive high-angle boundary, caused by the dendritic growth mechanism.     

Carburization of high-temperature steels: A simulation-based ranking of carburization resistance

Carburization is a failure mechanism affecting equipment, such as furnace tubes, operating at high temperatures. Carburization simulations were carried out for the heat-resistant steels referred to the API-530 standard by applying a model for carbon diffusion with the concurrent formation of alloy carbides. The calculated carbon and carbide volume fraction profiles were validated experimentally. The carburization layer is composed from M₂₃C₆ and M₇C₃ carbides. The time required for the carburization front to reach the mid-thickness of the tubes was used to characterize carburization resistance. The austenitic grades exhibit a higher carburization resistance than the ferritic grades at all temperatures. In the ferritic grades, alloy composition has a stronger effect at lower service temperatures (600 °C) where carburization resistance increases with Cr and Mo content. The acceleration of diffusion at high temperatures (800 °C) dominates the composition effects on carbon diffusion, and the carburization front is controlled by the formation of carbides, which in turn depends on the available amount of Cr in the steel. In the austenitic grades, the highest carburization resistance is exhibited by the stabilized grades 321 and 347 due to formation of TiC or NbC carbides respectively. Regarding the non-stabilized grades, carburization resistance is raised by addition of Mo (316 vs 304) and lower carbon (316L vs 316). The results of this study can be used for material selection for carburization resistance and for planning maintenance procedures for the timely replacement of tubes.     

Preferential distribution of chromium and nickel in the borided layer obtained on synthetic Fe-Cr-Ni alloys

Synthetic ferrous alloys containing chromium and/or nickel were prepared and borided at 1173 K with powders containing B₄C, KBF₄ and SiC for times varying from 20 to 60 h. The surface layers composed of borides of type (Fe, M)B and (Fe, M)₂B were characterized by means of X-ray diffraction, microscopic observations, analysis with the microprobe and microhardness measurements. A quantitative study was carried out on the differentiated distribution of chromium and nickel in the phases constituting the borided layer. The chromium spreads from the matrix towards the borided layer, where it is concentrated in the phase richest in boron (Fe, M)B. Nickel behaves in the opposite manner. Alloys without carbon were used in order to avoid the formation of an area containing carbides and boron carbides, situated between the borided layer and the matrix, which could influence chromium distribution. The distribution phenomenon is in accordance with what was found in the study of Fe-M-B ternary systems (M=Cr, Ni). The influence of chromium and nickel on the thickness, the morphology and the microhardness of the borided layer are discussed.     

Precipitates change of ferritic‐martensitic 11 % chromium steel under short‐term creep

A ferritic‐martensitic (FM) 11 % chromium steel with final heat treatment was subjected to a short‐term creep test at a stress of 150 MPa and 600 °C for 1100 h in order to study the change of precipitates in the steel during the creep test. Except for Nb‐rich metall carbides (MC, M₂₃C₆) and Laves phases, Fe‐W‐Cr‐rich M₆C (based on Fe₃W₃C) carbides forming during the creep test were also identified in the crept steel by electron diffraction and x‐ray diffraction in combination with energy dispersive x‐ray analysis of extraction carbon replicas. The identified M₆C carbides have a fcc crystal structure, a metallic element composition of approximately 44Fe, 32 W, and 20Cr in atomic %, and large sizes ranging from 100 nm to 300 nm in diameter. The M₆C carbides are a dominant phase in the crept steel. M₆X precipitates are generally not easy to form during high temperature creep, even if it is a long‐term creep, in ferritic‐martensitic 9–12 % chromium steels with a final heat treatment. The present work provides the evidence for the M₆C carbides forming during short‐term creep in ferritic‐martensitic high chromium steels. The formation of the M₆C carbides was discussed.     

Division of character zones and elements distribution of Fe3Al/Cr–Ni alloy fusion bonded joint

Abstract

A Fe₃Al/Cr–Ni alloy fusion bonded joint was divided into four character zones of a homogeneous mixture zone, a partial mixture zone, a partially fused zone and a heat affected zone. The microstructures, elements distribution and phase constitutions of the various character zones were analysed via metalloscope, SEM, electron probe microanalysis and X-ray diffraction. The results indicated that the microstructures were dissimilar in the different character zones. A 0·04–0·05 mm austenite rich band existed in the partial mixture zone. The diffusion of Fe, Al, Cr, Ni and C mainly occurred in fusion zone where Cr and Ni diffused into Fe₃Al to substitute some Fe on α ₁, α ₂, and β sublattices to form substitutional solid solution. The phase constitutions of Fe₃Al/Cr–Ni joint were Fe₃Al, γ-Fe, FeAl, NiAl, an unidentified Fe–C compound and an Fe–Cr–C compound (Cr₉Fe)₇C₃.     

The formation of chromium carbide during chromizing

The carbides formed during the chromizing of various types of carbon and chromium steels are considered in terms of the ternary phase diagram. A correlation is found between the carbide or carbides formed and a diffusion couple model. In low chromium, high carbon steels, an intermediate layer is formed which seems to be a (Fe,Cr)₃C cementite phase. The carbide which is formed on low carbon constructional steels depends on the detailed carbon and chromium profiles. Data found in the literature support the present interpretation.     

Microstructure of Fe-TiC surface composite produced by cast-sintering

Fe-TiC surface composite was prepared in situ on a surface of cast steel by means of cast-sintering technique. The microstructure of this material was investigated by means of SEM, electron probe and XRD. Results show that the TiC and (Fe,Cr)₇C₃ carbides in an iron matrix were achieved on the surface of cast steel during cast-sintering. From the top surface of sample to that of the master-steel, the concentration of Ti, Cr and Ni as well as the quantity of both TiC and (Fe,Cr)₇C₃ carbides decreased gradually, and the morphology of (Fe,Cr)₇C₃ transforms from strip-chunky into make-and-break reticulation. There was an excellent metallurgy-bond between the surface composite layer and the master-steel.     

Hot hardness of (Fe,Cr)3C and (Fe,Cr)7C3 carbides

Hot hardness was measured on the primary carbides, (Fe, Cr)₃C and (Fe, Cr)₇C₃, in unidirectionally solidified iron-carbon-chromium hypereutectic alloys with chromium more than 4.8 wt %. The hardness-temperature relation was represented by two Ito-Shishokin formulae,H _v =A(— BT), and thus was drawn by two lines on a semilogarithmic graph. The inflection temperature where the two lines intersected was found at 730 to 860 K for (Fe, Cr)₃C carbide containing 0 to 14 wt % Cr, increasing with an increase in the chromium concentration in the carbide, and at about 910 K for (Fe, Cr)₇C₃ carbide containing 36 to 76 wt % Cr. With increasing chromium concentration in each carbide, the hardness of the carbide increased and the thermal softening coefficients decreased. The effect of chromium on the hardness, the inflection temperature and the thermal softening coefficients was more pronounced for (Fe, Cr)₃C carbide than for (Fe, Cr)₇C₃ carbide. Each of the thermal softening coefficients,B ₁(T<T _t),B ₂(T>T _t), the inflection temperature,T _t, room-temperature hardness,H _v(T _RT), and the hardness atT _t,H _v(T _t), related linearly to the chromium concentration in the carbides, and hence the hot hardness of the carbides could be expressed as functions of temperature and chromium concentration in the carbides. The relationships betweenH _v(T _RT) andH _v(T _t) and between the thermal softening coefficient,B ₂, and the activation energy for creep,Q _c(kJ mol^–1), were represented by the following equations:H _v(T _t)0.7H _v(T _RT),B ₂=1.26/Q _c.     

Iron Carbides: Control Synthesis and Catalytic Applications in COx Hydrogenation and Electrochemical HER

Catalytic transformation of CO_x (x = 1, 2) with renewable H₂ into valuable fuels and chemicals provides practical processes to mitigate the worldwide energy crisis. Fe‐based catalytic materials are widely used for those reactions due to their abundance and low cost. Novel iron carbides are particularly promising catalytic materials among the reported ferrous catalysts. Recently, a series of strategies has been developed for the preparation of iron carbide nanoparticles and their nanocomposites. Control synthesis of FeC_x‐based nanomaterials and their catalytic applications in CO_x hydrogenation and electrochemical hydrogen evolution reaction (HER) are reviewed. The discussion is focused on the unique catalytic activities of iron carbides in CO_x hydrogenation and HER and the correlation between structure and catalytic performance. Future synthesis and potential catalytic applications of iron carbides are also summarized.     

Influence of 0.2 wt-%C on the aging response of Ti-15-3

Abstract

The effect of aging time and temperature on the microstructure and mechanical properties of Ti-15-3 (Ti – 3Cr – 3Sn – 3Al) with and without carbon addition has been studied. It has been found that carbon addition has a significant effect on the age hardenability and microstructural stability at higher aging temperatures in Ti-15-3, whereas it has a smaller effect at lower aging temperatures, where precipitation of α appears to influence precipitation of ω. The presence of carbides in Ti-15-3 accelerates the precipitation and inhibits the growth of α phase. The gettering of oxygen by the Ti₂C precipitates reduces the tendency of grain boundary α precipitation and improves the homogeneity of α precipitation. The significance of these observations is discussed in terms of the effect of the microstructural changes in quenched and aged samples associated with the presence of Ti₂C precipitates.     

Microstructural evolution in bainite,martensite, and δ ferrite of low activation Cr–2W ferritic steels

Abstract

The microstructural evolution in (2–15)Cr–2W–0·1C (wt-%) firritic steels after quenching, tempering, and subsequent prolonged aging was investigated, using mainly transmission electron microscopy. The steels examined were low induced radioactivation ferritic steels for fusion reactor structures. With increasing Cr concentration, the matrix phase changed from bainite to martensite and a dual phase of martensite and δ ferrite. During tempering, homogeneous precipitation of fine W₂C rich carbides occurred in bainite and martensite, causing secondary hardening between 673 and 823 K. With increasing tempering temperature, dislocation density decreased and carbides had a tendency to precipitate preferentially along interfaces such as bainite or martensite subgrain boundaries. During aging at high temperature, carbides increased in size and carbide reaction from W₂C and M₆C to stable M₂₃C₆ occurred. No carbide formed in δ ferrite. The precipitation sequence of carbides was analogous to that in conventional Cr–Mo steels.

MST/1049     

Influence of carbon on aging response and tensile properties of eutectoid beta titanium alloy Ti–13Cr

Abstract

The influence of carbon addition on the aging response of quenched Ti–13Cr (wt-%) has been investigated using hardness tests, tensile tests, optical microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It has been found that carbon refines beta grain size, leads to fine and homogenous alpha precipitation and reduces grain boundary alpha. The carbon addition accelerates the rate at which hardening occurs during aging and increases the peak hardness of the aged specimens. A significant improvement in room temperature tensile strength and ductility has also been achieved in the carbon containing alloy after aging at 500°C. The effects of carbon on the aging response appear to be attributed to dislocations introduced by carbides during quenching, elastic strain created in the matrix by carbides and gettering effect of Ti₂C carbides. The influence of each of those mechanisms has been demonstrated through experiments and the factors giving rise to the improvements in properties are also discussed in terms of the microstructural observations.     

Carbon diffusion in dissimilar joints between P91 and 12Cr1MoV steels welded by different consumables at high temperature

Three consumables: 9CrMoV(N), R31, and GTR-2CM are considered in welding P91 and 12Cr1MoV together. The stable phases and carbon activities of the involved materials were calculated by THERMO-CALC. Carbon diffusion after aging for varying times at 700°C was simulated by dispersed multiphase model in DICTRA. The usage of different weld metals causes different carbon concentration profiles near weld interfaces both on the P91 and 12Cr1MoV sides, driven by their carbon activity difference. Mole fractions of carbides varying with distance were investigated, showing that the formation of carbon-depleted zone (CDZ) and carbon-enriched zone (CEZ) is related to the dissolution and precipitation of M₂₃C₆ carbides. To validate the simulation results, the microstructure and hardness near the interface between P91 base and GTR-2CM weld metal were studied. Good agreements on the widths of CDZ and CEZ between modelled and experimental results were obtained.     

Effect of thermal exposure on the stability of carbides in Ni-Cr-W based superalloy

The microstructure evolutions of Ni-Cr-W based superalloy during thermal exposure have been investigated systematically. M₆C carbides in the alloy decompose into M₂₃C₆ carbides at temperatures from 650 to 1000 °C due to its high content of Cr. The M₆C carbides decompose dramatically from 800 to 900 °C. At temperatures up to 1000 °C, a few M₂₃C₆ carbides form on the surface of M₆C carbides. The decomposition behavior of primary M₆C can be explained by the following reaction: M₆C → M₂₃C₆ + Me (W, Ni, Cr, Mo). At temperatures below 900 °C, coarse lamellar M₂₃C₆ carbides precipitate at the grain boundaries. The carbide lamellae line almost perpendicular to the grain boundaries. While the temperature is above 1000 °C, discrete M₂₃C₆ carbides precipitate at the grain boundaries. Moreover, there are lots of small M₂₃C₆ particles precipitated around M₆C carbides from 650 to 1000 °C.     

Effect of heat treatment on microstructure and mechanical properties of Cr–Ni–Mo–Nb steel

Abstract

The microstructure and mechanical properties of a medium carbon Cr–Ni–Mo–Nb steel in quenched and tempered conditions were investigated using transmission electron microscopy (TEM), X-ray analysis, and tensile and impact tests. Results showed that increasing austenitisation temperature gave rise to an increase in the tensile strength due to more complete dissolution of primary carbides during austenitisation at high temperatures. The austenite grains were fine when the austenitisation temperature was <1373 K owing to the pinning effect of undissolved Nb(C,N) particles. A tensile strength of 1600 MPa was kept at tempering temperatures up to 848 K, while the peak impact toughness was attained at 913 K tempering, as a result of the replacement of coarse Fe rich M₃C carbides by fine Mo rich M₂C carbides. Austenitisation at 1323 K followed by 913 K tempering could result in a combination of high strength and good toughness for the Cr–Ni–Mo–Nb steel.