Metallographic observations during the sintering of BM2 type of high speed steels

Metallographic changes during the sintering of BM2 type of high speed steels have been investigated by scanning electron microscopy, in the range of optimum sintering to oversintering. The primary carbides observed are M₆C and a small quantity of MC; in the oversintered structure an additional carbide with eutectic morphology was seen. It is a chromium and molybdenum rich phase in BM2+ 0 to 4% cobalt (0.9 to 1.2% carbon) alloy, whereas in BM2+ 8% cobalt (0.9% carbon) the eutectic phase is MC. Under certain conditions M₃C was also detected in the post-sintered alloy.     

Carbide types in an advanced microalloyed bainitic/ferritic Cr–Mo Steel – TEM observations and thermodynamic calculations

The strength and toughness of low alloyed ferritic/bainitic steels depend on their microstructure, which evolves during thermo‐mechanical treatments along the processing chain. Chromium‐molybdenum steel microstructures are complex. Therefore, only a limited number of attempts have been made to fully characterize carbide populations in such steels. In the present work, analytical transmission electron microscopy is employed to study the microstructure of a low alloyed chromium‐molybdenum steel, which features ferritic (F, mainly α‐iron and niobium‐carbides) and bainitic (B, α‐phase, dislocation, grain/subgrain boundaries, various M_xC_y carbides) regions. The crystal structure and chemical nature of more than 200 carbides are determined and their distributions in the two microstructural regions are analyzed. The present work shows how particles can be identified in an effective manner and how the microstructural findings can be interpreted on the basis of thermodynamic calculations.     

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     

The influence of vanadium on fracture toughness and abrasion resistance in high chromium white cast irons

The influence of vanadium on wear resistance under low-stress conditions and on the dynamic fracture toughness of high chromium white cast iron was examined in both the ascast condition and after heat treatment at 500 °C. A vanadium content varying from 0.12 to 4.73% was added to a basic Fe-C-Cr alloy containing 2.9 or 19% Cr. By increasing the content of vanadium in the alloy, the structure became finer, i.e. the spacing between austenite dendrite arms and the size of massive M₇C₃ carbides was reduced. The distance between carbide particles was also reduced, while the volume fraction of eutectic M₇C₃ and V₆C₅ carbides increased. The morphology of eutectic colonies also changed. In addition, the amount of very fine M₂₃C₆ carbide particles precipitated in austenite and the degree of martensitic transformation depended on the content of vanadium in the alloy. Because this strong carbide-forming element changed the microstructure characteristics of high chromium white iron, it was expected to influence wear resistance and fracture toughness. By adding 1.19% vanadium, toughness was expected to improve by approximately 20% and wear resistance by 10%. The higher fracture toughness was attributed to strain-induced strengthening during fracture, and thereby an additional increment of energy, since very fine secondary carbide particles were present in a mainly austenitic matrix. An Fe-C-Cr-V alloy containing 3.28% V showed the highest abrasion resistance, 27% higher than a basic Fe-C-Cr alloy. A higher carbide phase volume fraction, a finer and more uniform structure, a smaller distance between M₇C₃ carbide particles and a change in the morphology of eutectic colonies were primarily responsible for improving wear resistance.     

Thermal-induced evolution of secondary phases in Cr–Mo–V low alloy steels

Four low alloy steels with different contents of molybdenum and vanadium were investigated. The steels were annealed at 773, 793, 853, 873, 933, 973, and 993 K for 500, 1000, 3000, and 10000 h. Techniques of transmission electron microscopy and thermodynamic calculations (ThermoCalc) were used to characterise influence of the steel bulk composition and the annealing conditions on evolution of carbides M₃C, M₂C, M₇C₃, M₂₃C₆, M₆C, and MC (M=metallic element). Changes in structure types and metal compositions of the carbides were characterised in detail. The work was done with the intention to obtain more information about the secondary phase evolution in low alloy steels used in energy industries.     

Effects of vanadium on upper-nose temper embrittlement and other Mechanical properties of Cr–Ni–Mo low-alloy steels

Abstract

Large components manufactured from Cr–Mo–Ni low-alloy steels are usually heavily tempered for the purpose of stress relieving, with resultant undesirable loss of strength and the inception of upper-nose temper embrittlement (UNTE). This paper describes an investigation on the effects of vanadium additions and of variation in the molybdenum content on the properties of these heavily tempered steels. It is shown that the addition of vanadium to these steels leads to a substantial improvement in their strength without impairment of their ductility and toughness, and also to a marked improvement in their resistance to UNTE. An increase in the molybdenum content of the steel from 0·5 to 1·0% leads to a moderate improvement in its strength, but has an aggravating effect on its susceptibility to UNTE, as a result of an increase in the coarsening rate of the grain boundary carbides and the formation of unfavourable M₂₃C₆ and M_aC_b molybdenum-rich large carbides.

MST/390     

Metallographic changes in the sintering of grade T high speed steels in an industrial atmosphere and vacuum

The metallographic changes taking place in three T grade steels, T42, T15 and T1 in the range of optimum sintering temperature to oversintering in vacuum and in an industrial atmosphere — base nitrogen — have been investigated using SEM and EDS techniques. M₆C and MC primary carbides have been observed for vacuum sintering and MX carbonitrides instead of MC carbides were found in the specimens sintered in the atmosphere. Small amounts of an eutectic carbide rich in Cr and Fe have been observed at the optimum sintering temperature. By oversintering in vacuum different type of eutectic carbides can be observed: MC, needle shape, M₆C, but only M₆C type eutectic carbide have been observed by oversintering the samples in the industrial atmosphere.     

Interface temperature measurement of M2C and M6C eutectic carbides in the Fe–Mo–C system

The High speed cast iron, which is used for hot rolling parts, needs high fracture toughness and wear resistance. To improve these properties, the control of eutectic carbides, M₃C, M₇C₃,M₆C and MC is important by adding elements such as Cr, W, V and Mo.

The aim of this study is to estimate which carbide will solidify under certain solidification conditions and compositions. This prediction criterion can be gained by measuring the interface temperature of each carbide in various samples with different solute elements, composition and growth rate.

In this report, the solidified temperature of γ + M₂C and γ + M₆C eutectic carbide in the Fe–Mo–C ternary system in the composition range near to the eutectic monovariant line, was measured during the unidirectional solidiication process. The relationship between solidified interface temperature and growth rate was obtained. In eutectic solidification along the γ + M₆C monovariant line, a coefficient of undercooling, the k value, was obtained.

The authors have already measured the k values of other eutectic carbides, such as γ + M₃C, austenite + M₇C₃, and γ + VC in Fe–Cr–C and Fe–V–C system. The paper also discusses the relationships between these properties of eutectic carbides.     

Interface temperature measurement of M2C and M6C eutectic carbides in the Fe–Mo–C system

The High speed cast iron, which is used for hot rolling parts, needs high fracture toughness and wear resistance. To improve these properties, the control of eutectic carbides, M₃C, M₇C₃, M₆C and MC is important by adding elements such as Cr, W, V and Mo.The aim of this study is to estimate which carbide will solidify under certain solidification conditions and compositions. This prediction criterion can be gained by measuring the interface temperature of each carbide in various samples with different solute elements, composition and growth rate.In this report, the solidified temperature of γ+M₂C and γ+M₆C eutectic carbide in the Fe–Mo–C ternary system in the composition range near to the eutectic monovariant line, was measured during the unidirectional solidification process. The relationship between solidified interface temperature and growth rate was obtained. In eutectic solidification along the γ+M₆C monovariant line, a coefficient of undercooling, the k value, was obtained.The authors have already measured the k values of other eutectic carbides, such as γ+M₃C, austenite+M₇C₃, and γ+VC in Fe–Cr–C and Fe–V–C system. The paper also discusses the relationships between these properties of eutectic carbides.     

Management of composition cathodic products in the electrolysis of molybdenum‐, tungsten‐ and carbon‐ bearing halogenide‐oxide and oxide melts

It is shown that the cathode products of electrolysis of melts based on a eutectic mixture of sodium chloride and lithium fluoride as well as melts based on sodium tungstate in which dissolved oxides of molybdenum (VI) or tungsten (VI), molybdate, tungstate and lithium or sodium carbonates are molybdenum, tungsten, their bronzes and carbides, carbon. It is established that the phase composition of electrolysis products is determined by the concentration of carbonate in the melt. Particular conditions of plating coating of molybdenum and tungsten carbides on carbon, nickel and copper materials are determined. Molybdenum carbide coatings of electrolyte Na₂WO₄–Li₂MoO₄–Li₂CO₃ are deposited at equality (within 2.5 mol%) of concentrations molybdate and lithium carbonate. However, their concentrations should not exceed 10 mol%. At lower concentrations of molybdate in the precipitate are detected carbon, molybdenum, molybdenum carbide, and at high concentrations – molybdenum oxides. At lower concentrations of carbonate in the sediment dominates molybdenum and at large concentrations mainly free carbon is released. More affordable industrial reagent‐source of molybdenum is its oxide.     

Microstructures and high temperature properties of spray formed niobium‐containing M3 high speed steel

The billets of M3 high speed steel (HSS) with or without niobium addition were prepared via spray forming and forging, and the corresponding microstructures, properties were characterized and analysed. Finer and uniformly‐distributed grains without macrosegregation appear in the as‐deposited high speed steel that are different to the as‐cast high speed steel, and the primary austenite grain size can be decreased with 2% niobium addition. Niobium appears in primary MC‐type carbides to form Nb₆C₅ in MN2 high speed steel, whereas it contributes less to the creation of eutectic M₆C‐type carbides. With same treatments to forged MN2 high speed steel and M3 high speed steel, it is found that the peak hardness of these two steels are almost the same, but the temper‐softening resistance of the former is better. With higher high‐temperature hardness of the forged MN2 high speed steel, its temper softening above 600 °C tends to slow down, which is related to the precipitation of the secondary carbides after tempering. A satisfactory solid solubility of Vanadium and Molybdenum can be obtained by Nb substitution, precipitation strengthening induced by larger numbers of nano‐scaled MC and M₂C secondary carbides accounts for the primary role of determining higher hardness of MN2 high speed steel. The results of the wear tests show that the abrasive and adhesive wear resistance of MN2 high speed steel can be improved by the grain refinement, existence of harder niobium‐containing MC carbides, as well as solute strengthening by more solute atoms. The oxidational wear behavior of MN2 high speed steel can be markedly influenced by the presence of the high hardness and stabilization of primary niobium‐containing MC‐type carbides embedded in the matrix tested at 500 °C or increased loads. The primary MC carbides with much finer sizes and uniform distribution induced by the combined effects of niobium addition and atomization/deposition would be greatly responsible for the good friction performance of the forged MN2 high speed steel.     

Processing of P/M T15 high speed steels by mould casting using thermosetting binders

In this work we present the application to a T15 high speed steel of a modified metal injection moulding process based on the use of a thermosetting resin. This method has been successfully applied to produce 316L stainless steels and M2 HSS. The main characteristic of this manufacturing method is that the slurry (polymer and metal powder) is introduced into the mould at room temperature and afterward is heated at 90°C in order to polymerise the resin. We have optimised the powder-binder formulation and the best thermal debinding cycle by means of thermogravimetric analysis. Since the microstructure and properties of the HSS is very sensitive to the sintering temperature, its effect on the density, hardness, transverse rupture strength and microstructure was investigated. The mechanical properties obtained are in good agreement with other HSS parts manufactured by conventional MIM. During the sintering process it has been identified vanadium carbide (MC) and tungsten carbide (M₆C) that are homogeneously distributed on the steel matrix.     

Precipitation in 9Cr–1Mo steel after creep deformation

The carbides present after creep testing a 9Cr–1Mo steel at 566 °C over a range of stress levels giving rupture times of up to 7300 h have been characterized and identified using a transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron diffraction. The initial carbide precipitates present were M₇C_3, (NbV)C and VC and it was determined that M₆C carbide precipitates were present in all specimens after elevated temperature exposure for greater than approximately 1700 h. No precipitation of M₂₃C₆ was detected. The evolutionary sequence from the initially present carbides during high temperature exposure involved the formation of the stable M₆C carbide directly, without the intermediate formation of M₂₃C₆, as is reported to occur in other Cr–Mo steels.     

Si影响M2高速钢中共晶碳化物的精细研究

通过金相、扫描电镜、X射线衍射、能谱分析等方法对添加不同Si量的M2高速钢中的共晶碳化物进行了精细研究。结果表明,添加1%Si后,M2高速钢铸态组织中共晶碳化物的类型和形貌都没有明显变化,仍以层片状M2C碳化物为主;添加2%和3%Si后,铸态组织中的共晶碳化物变为"鱼骨"状M6C碳化物,层片状M2C共晶碳化物已完全消失;此外,随着含Si量的增加,高速钢铸态组织枝晶间距减小。     

A Study of Modification of M2 Cast High Speed Steel

M2 cast high speed steel was inoculated by addition of rare earth(RE)‐Al‐N, network eutectic carbides were eliminated, matrix structures were refined and the segregation of tungsten and molybdenum elements were relieved. In the condition that the hardness did not decrease, impact toughness obviously increased. Quenching at 1180 °C and three‐times tempering at 560 °C, the hardness of M2 cast high speed steel kept 65~66HRC, impact toughness reached 21.3J/cm². Modified M2 cast high speed steel had excellent thermal fatigue resistance and high temperature wear resistance. Roll made in modified M2 cast high speed steel had excellent service effect using in slit rolling mill stand of hot rolling bar mill.     

Decomposition modes of austenite in 9Cr–W–V–Ta reduced activation ferritic–martensitic steels

The present paper presents the results of an extensive electron microscopy investigation on the decomposition modes of high temperature austenite in 9Cr–W–V–Ta reduced activation ferritic–martensitic steels. Although the displacive martensitic transformation is predominant on austenitisation, low volume fraction of Fe rich M₃C or M₂₃C₆ precipitates formed, when the tungsten content exceeded 1 wt-%. The compositional inhomogeneity introduced in the austenite by the nature, chemistry and kinetics of dissolution of the pre-existing carbides is dependent on the steel composition and austenitisation conditions. The extent of repartitioning of tungsten between M₂₃C₆ and ferrite largely influences the kinetics of austenite and martensite transformation, for the same austenitisation conditions. Supporting evidence from calorimetry analysis is also presented.     

On the microstructure and mechanical properties of high-speed steels

The microstructure of high-speed steels consists of a martensitic matrix with a dispersion of two sets of carbides. These carbides are usually known as primary and secondary carbides. The role of the primary carbides has been reported to be of no importance in strengthening the steels, due to their large size and large interparticle spacing. The present authors have studied the role of the primary carbides on the wear of high-speed steels and found them to be of no importance, and under certain conditions contributing to higher wear rates. It has been shown analytically and experimentally that in quenched and tempered high-speed steels, the precipitation of the secondary hardening carbide (cubic M₂C type) is the main reason for the improved strength and wear resistance. This shows that the secondary hardening phenomenon of high-speed steels is a direct result of the hardening caused by the precipitation of the cubic M_2C-type carbide. The present study has estimated that at peak hardness the volume fraction of secondary hardening carbides is approximately 20%. The measured strength of high-speed steels was found to be lower than the theoretically calculated strength due to non-homogeneous precipitation of the secondary hardening carbides. Areas which were observed to be free from secondary hardening carbides are real and are not artefacts. It has been shown that the strength of high-speed steel in the region of peak hardness depends primarily on the precipitation of the secondary hardening carbide and secondarily on martensitic strengthening.     

Carbides in iron-rich Fe-Mn-Cr-Mo-Al-Si-C systems

Duplex microstructures of iron-base superalloys, consisting of an austenitic matrix and a M₇C₃ carbide, can be produced within the Fe-Mn-Cr-Mo-Al (Si)-C systems. The stability regions of the carbides were inspected by means of isothermal sections of alloys in the quinary combination Fe-Mn-Cr-Mo-C for 70 at% metal and 30 at % carbon. For 35 at % iron the competing carbides are found to be M₂C, M₃C and the molybdenum cementite (MoFe₂C) in the arc-melted state, with M₂3C₆ in the annealed state. In the quaternary system, Fe-Mn-Mo-C, a M₂C carbide forms, presumaby derived from a solid solution carbide, (Mn, Mo)₂C. In extracted carbides of cast alloys containing Fe-Mn-Cr-Mo-Al (Si)-C a considerable amount of the -phase carbide occurs.     

Morphology and microstructure of M<Subscript>2</Subscript>C carbide formed at different cooling rates in AISI M2 high speed steel

In as-cast structure of AISI M2 high speed steel, M₂C carbide prevails, the morphology of which has crucial influence on distribution and dimension of carbides in final products. In this study, the morphology and microstructure of M₂C formed at different cooling rates have been investigated by scanning electron microscope, X-ray diffraction, transmission electron microscope, and electron back-scatter diffraction. The results show that the morphology of M₂C carbide changes from the plate-like type to the fibrous one with increasing cooling rates. Surprisingly, the microstructure between plate-like and fibrous M₂C is significantly different. Twining and stacking faults are observed in the plate-like M₂C, which is supported by great misorientations between adjacent carbides. However, no planar faults are identified in fibrous M₂C and the carbides in one colony have almost identical orientation. It is expected that plate-like M₂C grows as a faceted phase, while fibrous M₂C formed at high cooling rates is likely a non-faceted phase. The difference of liquid/solid interface structure is supposed to result in the morphology change of M₂C.     

Effects of co-addition of titanium and boron on microstructure of superplastic Cr–Mo steels

Abstract

The effects of titanium and boron on the microstructure of a low alloyed Cr–Mo steel with 0·6 wt-%C have been investigated by comparison with a steel containing only titanium and a steel free from both titanium and boron. Each of the steels was subjected to thermomechanical treatment and annealed at 700°C, resulting in small grains of size a few micrometres. The steel containing both titanium and boron possessed the smallest ferrite grains and M₃C carbides of the three examined. This is attributed to a fine dispersion of borides (TiB₂ ) and borocarbides (Ti(C,B)) of size 10 nm in the ferrite matrix through the pinning effect. At the grain boundaries small carbide particles were present which were effective in inhibiting grain boundary migration. The extremely fine borides and/or borocarbides were useful in suppressing intragranular deformation of ferrite grains due to precipitation hardening. This may have assisted in promoting grain boundary sliding, resulting in superior superplastic elongation.