Effect of Nitrogen and Niobium on the Structure and Secondary Hardening of Super Hard High Speed Tool Steel

High‐speed steels have been used mostly for multi‐point cutting tools and for plastic working tools. High speed steels are ferrous based alloys of the Fe‐C‐X multi‐component system where X represents a group of alloying elements comprising mainly Cr, W or Mo, V, and Co. The properties of these steels can be improved by modifying their chemical composition or the technology of their production. One of the new trends in modifying the tool steels chemical composition consists in the addition of niobium and nitrogen. In this work, the effects of niobium and nitrogen on morphology of carbides and secondary hardening temperature of investigated high speed tool steels were studied. This experimental work shows that, the conventional ingots have many types of carbides of different shapes and sizes precipitate on the boundary together with thick needle like carbides. On the contrary, for nitrogen steel, the nitrogen alloying leads to form dense, fine and well distributed microstructure. While, on the case of niobium alloying, single carbide (MC), and different types of eutectic carbides were precipitated which have a major effect on the secondary hardening temperature.     

Structure and properties of high-temperature austenitic steels for superheater tubes

The structure and properties of high-temperature austenitic steels intended for superheater tubes are analyzed. Widely used Kh18N10T (AISI 304) and Kh16N13M3 (AISI 316) steels are found not to ensure a stable austenitic structure and stable properties during long-term thermal holding under stresses. The hardening of austenitic steels by fine particles of vanadium and niobium carbides and nitrides and γ′-phase and Fe₂W and Fe₂Mo Laves phase intermetallics is considered. The role of Cr₂₃C₆ chromium carbides, the σ phase, and coarse precipitates of an M ₃B₂ phase and a boron-containing eutectic in decreasing the time to failure and the stress-rupture strength of austenitic steels is established. The mechanism of increasing the stress-rupture strength of steels by boron additions is described. The chemical compositions, mechanical properties, stress-rupture strength, and creep characteristics of Russian and foreign austenitic steels used or designed for superheater tubes intended for operation under stress conditions at temperatures above 600°C are presented. The conditions are found for increasing the strength, plasticity, and thermodeformation stability of austenite in steels intended for superheater tubes operating at 700°C under high stresses for a long time.     

Equilibrium Model of Precipitation in Microalloyed Steels

The formation of precipitates during thermal processing of microalloyed steels greatly influences their mechanical properties. Precipitation behavior varies with steel composition and temperature history and can lead to beneficial grain refinement or detrimental transverse surface cracks. This work presents an efficient computational model of equilibrium precipitation of oxides, sulfides, nitrides, and carbides in steels, based on satisfying solubility limits including Wagner interaction between elements, mutual solubility between precipitates, and mass conservation of alloying elements. The model predicts the compositions and amounts of stable precipitates for multicomponent microalloyed steels in liquid, ferrite, and austenite phases at any temperature. The model is first validated by comparing with analytical solutions of simple cases, predictions using the commercial package JMat-PRO, and previous experimental observations. Then it is applied to track the evolution of precipitate amounts during continuous casting of two commercial steels (1004 LCAK and 1006Nb HSLA) at two different casting speeds. This model is easy to modify to incorporate other precipitates, or new thermodynamic data, and is a useful tool for equilibrium precipitation analysis.     

Effect of carbon concentration on precipitation behavior of M<Subscript>23</Subscript>C<Subscript>6</Subscript> carbides and MX carbonitrides in martensitic 9Cr steel during heat treatment

The distributions and precipitated amounts of M₂₃C₆ carbides and MX-type carbonitrides with decreasing carbon content from 0.16 to 0.002 mass pct in 9Cr-3W steel, which is used as a heat-resistant steel, has been investigated. The microstructures of the steels are observed to be martensite. Distributions of precipitates differ greatly among the steels depending on carbon concentration. In the steels containing carbon at levels above 0.05 pct, M₂₃C₆ carbides precipitate along boundaries and fine MX carbonitrides precipitate mainly in the matrix after tempering. In 0.002 pct C steel, there are no M₂₃C₆ carbide precipitates, and instead, fine MX with sizes of 2 to 20 nm precipitate densely along boundaries. In 0.02 pct C steel, a small amount of M₂₃C₆ carbides precipitate, but the sizes are quite large and the main precipitates along boundaries are MX, as with 0.002 pct C steel. A combination of the removal of any carbide whose size is much larger than that of MX-type nitrides, and the fine distributions of MX-type nitrides along boundaries, is significantly effective for the stabilization of a variety of boundaries in the martensitic 9Cr steel.     

Thermal treatment improving creep properties of nitrogen-added Mod.9Cr-1Mo steels

Generation IV reactors are being developed to produce a reliable energy safely and with an economic benefit, because nuclear energy is being seriously considered to meet the increasing demand for a world-wide energy supply without environmental effects. Ferritic/martensitic steels are attracting attention as candidate materials for the Gen-IV reactors due to their high strength and thermal conductivity, low thermal expansion, and good resistance to corrosion. In recent years, new ferritic/martensitic steels have been developed for ultra supercritical fossil power plants through advanced technologies for steel fabrication. The microstructural stability of these materials for the pressure vessel, cladding and core structure of the VHTR and SFR is very important. Nitrogen is a precipitation hardening element, and the thermal stability of nitrides is superior to that of carbides. So the formation of nitrides may improve the thermal stability of the microstructure and eventually increase the creep rupture strength of high Cr steels. The effect of nitrogen on the creep rupture strength and microstructure evolution of nitrogen-added Mod.9Cr-1Mo steels has been studied. Creep testing was carried out at 873 and 923 K under constant load conditions. The optimum controlled Cr₂X precipitates were developed by special heat treatment, and they were not dissolved after a creep deformation. These fine and stable Cr₂X precipitates contributed to the increase of the creep rupture strength. The prior austenite grain size and martensite lath width were decreased by the resultant stable nitrides.     

Carbides in high-speed steels containing silicon

The effects of silicon additions up to 3.5 wt pct on the as-cast carbides, as-quenched carbides, and as-tempered carbides of high-speed steels W3Mo2Cr4V, W6Mo5Cr4V2, and W9Mo3Cr4V were investigated. In order to further understand these effects, a Fe-16Mo-0.9C alloy was also studied. The results show that a critical content of silicon exists for the effects of silicon on the types and amount of eutectic carbides in the high-speed steels, which is about 3, 2, and 1 wt pct for W3Mo2Cr4V, W6Mo5Cr4V2, and W9Mo3Cr4V, respectively. When the silicon content exceeds the critical value, the M₂C eutectic carbide almost disappears in the tested high-speed steels. Silicon additions were found to raise the precipitate temperature of primary MC carbide in the melt of high-speed steels that contained d-ferrite, and hence increased the size of primary MC carbide. The precipitate temperature of primary MC carbide in the high-speed steels without d-ferrite, however, was almost not affected by the addition of silicon. It is found that silicon additions increase the amount of undis-solved M₆C carbide very obviously. The higher the tungsten content in the high-speed steels, the more apparent is the effect of silicon additions on the undissolved M₆C carbides. The amount of MC and M₂C temper precipitates is decreased in the W6Mo5Cr4V and W9Mo3Cr4V steels by the addition of silicon, but in the W3Mo2Cr4V steel, it rises to about 2.3 wt pct.     

Niobium Carbide Precipitation in Microalloyed Steel

The precipitation of niobium carbo‐nitrides in the austenite phase, interphase and ferrite phase of microalloyed steel was assessed by a critical literature review and a round table discussion. This work analyses the contribution of niobium carbide precipitates formed in ferrite in the precipitation hardening of commercially hot rolled strip. Thermodynamics and kinetics of niobium carbo‐nitride precipitation as well as the effect of deformation and temperature on the precipitation kinetics are discussed in various examples to determine the amount of niobium in solid solution that will be available for precipitation hardening after thermomechanical rolling in the austenite phase and successive phase transformation.     

Analysis of the Strain‐Induced Martensitic Transformation of Retained Austenite in Cold Rolled Micro‐Alloyed TRIP Steel

The stability of retained austenite and the kinetics of the strain‐induced martensitic transformation in micro‐alloyed TRIP‐aided steel were obtained from interrupted tensile tests and saturation magnetization measurements. Tensile tests with single specimens and at variable temperature were carried out to determine the influence of the micro‐alloying on the M_s^σ temperature of the retained austenite. Although model calculations show that the addition of the micro‐alloying elements influences a number of stabilizing factors, the results indicate that the stability of retained austenite in the micro‐alloyed TRIP‐aided steels is not significantly influenced by the micro‐alloying. The kinetics of the strain‐induced martensitic transformation was also not significantly influenced by addition of the micro‐alloying elements. The addition of micro‐alloying elements slows down the autocatalytic propagation of the strain‐induced martensite due to the increase of the yield strength of retained austenite. The lower uniform elongation of micro‐alloyed TRIP‐aided steel is very likely due to the presence of numerous precipitates in the microstructure and the pronounced ferrite grain size refinement.     

Changes in Tempering and its Effect on Precipitation Behaviour in a Hot‐work Tool Steel

The microstructural characteristics of the hot‐worked and subsequently tempered tool steel grade X38CrMoV5‐1 was studied as a function of the cooling rate using transmission electron microscopy and three‐dimensional atom probe. According to the continuous cooling transformation diagram different cooling rates were chosen to adjust a fully martensitic or mixed microstructure consisting of martensite and bainite. The sample with the highest cooling rate exhibited a martensitic structure with nanometre sized secondary hardening carbides of the type M₃C, M₂C, M₇C₃, and MC. M₃C and M₂C were not stable and transformed to M₇C₃ as the cooling rate decreased. Furthermore, with decreasing cooling rates an increasing number of M₇C₃ precipitates are particularly present at former austenite grain boundaries as well as martensite and bainite lath boundaries, which strongly affects the mechanical properties.     

Influence of Cerium on Solidification Microstructure of M2 High Speed Steel

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As-cast carbides in high-speed steels

The spatial distribution and structure of as-cast carbides and the effects of W, Mo, and V content on the morphology and amount of as-cast carbides in high-speed steels were studied systematically. It was shown that increasing the Mo and decreasing the W content led to a decrease in the amount of total eutectic carbide and an increase in the MC and M₂C carbides. The eutectic morphology changed from skeletal to platelike when the content of Mo increased. The presence of V favored not only the formation of MC carbide but also the formation of M₂C carbide and reduced the formation of M₂C carbide. Increasing V led to an increase in the size of the eutectic carbides.     

Globular Structure of M2 High Speed Steel by Thermomechanical Treatment in the Semisolid State

The globular structure of M2 high speed steel in the rolled ‐ annealed and as cast conditions was investigated in the semisolid state. Metallographic observations resulted in globular austenite particles that were surrounded by a liquid phase. Dissolution of various carbides in the austenite phase at semisolid temperatures led to grain boundary liquation and formation of near‐spherical solid grains in a liquid matrix. Therefore, at the semisolid state, the solid particles were free from carbides. MC‐ type and M₆C‐ type eutectic carbides re‐ precipitated at the grain boundaries during cooling of the samples from the semisolid temperature. The variation of shape factor versus holding time and holding temperature was examined. A transition value for shape factor changes in high speed steels was achieved. The growth rate constants of the Ostwald ripening and the coalescence mechanisms were calculated by using the experimentally determined rate constant. It was observed that less liquid droplets were enclosed inside the solid particles compared with non‐ferrous alloys. Besides, it has been shown that at high solid fraction, the Ostwald ripening mechanism plays a prominent role in the coarsening phenomenon in comparison with the coalescence mechanism. Grains can rotate and arrange low misorientation with each other at high liquid contents, therefore low energetic grain boundaries form between these grains. These grain boundaries play an important role in the coalescence mechanism.     

Laser melting of T1-high speed tool steel

Metallographic (optical, TEM, SEM), spectroscopic, and microhardness investigations of Tl high speed tool steel heated by neodymium-pulsed laser (NPL) are described. Martensite, retained aus-tenite, delta (δ)-ferrite, M₆C carbides, and cellular segregations of W, V, and Cr were observed in the laser-melted zone. The high chemical homogeneity and fine structure of the melted zone were attrib-uted to high cooling rates due to the short interaction time with the neodymium-pulsed radiation and relatively small volume of the melted material. Fine precipitates, cellular M₆C carbides, and plate-like MC carbides were formed in the melted zone during tempering. An increase in micro-hardness of the laser-melted zone with tempering temperature was observed and attributed to these precipitates and the transformation of the retained austenite. Formerly Visiting Scientist, University of California, Berkeley.     

Paper,honoured with the Sir Charles Hatchett Award by the Institute of Metals,London: Developments in high speed tool steels

This paper describes a research programme at the Austrian School of Mines (Montanuniversität) at Leoben, carried out since 1981 in cooperation with the Max-Planck-Institute for metals research in Stuttgart, on the fundamentals of alloy design for high speed tool steels. Among the results, the development of niobium-alloyed grades has an important place. Controlled solidification studies with a gradient technique have clarified the influence of various alloying elements on the as-cast microstructure of ledeburitic tool steels. A procedure for accurate quantitative metallography in SEM, combined with EDX and STEM-EDX analysis of the chemical compositions of the carbide and matrix phases, has led to a quantitative model for the performance of high speed steels in metal cutting tools, in which the contributions of carbides and of the matrix are combined using empirically determined weight factors. An important role is played by the saturation of the matrix with vanadium and other carbide formers which are essential for secondary hardening. This saturation is related to the way in which these carbide formers are present in the annealed structure; this in turn is influenced decisively by the solidification path (via M₆C or M₂C) of the alloy. On the basis of these concepts, low alloyed, niobium-containing economy grades have been developed whose performance is comparable to that of commercial high speed steels, and perspectives for the development of economic super high speed steels with niobium as an alloying element are indicated.     

Effects of alloying additions and austenitizing treatments on secondary hardening and fracture behavior for martensitic steels containing both Mo and W

The effects of alloying additions and austenitizing treatments on secondary hardening and fracture behavior of martensitic steels containing both Mo and W were investigated. The secondary hardening response and properties of these steels are dependent on the composition and distribution of the carbides formed during aging (tempering) of the martensite, as modified by alloying additions and austenitizing treatments. The precipitates responsible for secondary hardening are M₂C carbides formed during the dissolution of the cementite (M₃C). The Mo-W steel showed moderately strong secondary hardening and delayed overaging due to the combined effects of Mo and W. The addition of Cr removed secondary hardening by the stabilization of cementite, which inhibited the formation of M₂C carbides. The elements Co and Ni, particularly in combination, strongly increased secondary hardening. Additions of Ni promoted the dissolution of cementite and provided carbon for the formation of M₂C carbide, while Co increased the nucleation rate of M₂C carbide. Fracture behavior is interpreted in terms of the presence of impurities and coarse cementite at the grain boundaries and the variation in matrix strength associated with the formation of M₂C carbides. For the Mo-W-Cr-Co-Ni steel, the double-austenitizing at the relatively low temperatures of 899 to 816 °C accelerated the aging kinetics because the ratio of Cr/(Mo + W) increased in the matrix due to the presence of undissolved carbides containing considerably larger concentrations of (Mo + W). The undissolved carbides reduced the impact toughness for aging temperatures up to 510 °C, prior to the large decrease in hardness that occurred on aging at higher temperatures.     

The effects of MO and W on solidification of high speed steels

The effects of systematic variations in Mo content, W content, and the Mo:W ratio upon the freezing process and as-cast carbide morphology of high speed steels were studied for four series of alloys encompassing the nominal composition ranges of AISI type M2 (6 W-5 Mo-4Cr-2V-0.85C) and MIO (0W-8Mo-4Cr-2 V-0.85C) high speed steels. Thermal analysis, metallographic examination, and quantitative metallography were used to characterize these effects. The Hquidus, peritectic, and eutectic reactions were similarly influenced by molybdenum and tungsten, the peritectic temperature being strongly depressed by additions of either element. The types of carbides found in the as-cast structures did not vary, but the amount of feathery eutectic carbide (a layered structure of MC and M₆C) was directly relatedto the total Mo plus W content. The amount of isolated vanadium-rich MC type carbide was seen to increase as the amount of feathery eutectic decreased, and also varied with the Mo:W ratio.     

Solidification of high-speed tool steels

Gradient solidification and differential thermal analysis (DTA) experiments were used to study the process of solidification and the solidification microstructure of 11 alloys comprising the composition range of customary commercial high-speed steels (with the exception of cobalt-alloyed grades). Also included are a number of experimental high-speed steels alloyed with niobium. The results include the effects of alloy composition and cooling rate on the width of the solidification interval and on the sequence of the solidification reactions; the types of eutectics formed (austenite with M₆C, M₂C, or MC) and their volume fractions; the chemical compositions of the ledeburitic and primary carbides; and the relation between the chemistry of the carbides and that of the melt. Special attention is given to the formation and composition of heterogeneously nucleated primary MC particles and to the chemistry and stability of eutectic M₂C, which is important as a precursor to MC and M₆C in the microstructure of finished (hot-worked and heat-treated) material.     

Effects of alloying elements on mechanical and fracture properties of base metals and simulated heat-affected zones of SA 508 steels

This study was aimed at developing low-alloy steels for nuclear reactor pressure vessels by investigating the effects of alloying elements on mechanical and fracture properties of base metals and heat-affected zones (HAZs). Four steels whose compositions were variations of the composition specification for SA 508 steel (class 3) were fabricated by vacuum-induction melting and heat treatment, and their tensile properties and Charpy impact toughness were evaluated. Microstructural analyses indicated that coarse M₃C-type carbides and fine M₂C-type carbides were precipitated along lath boundaries and inside laths, respectively. In the steels having decreased carbon content and increased molybdenum content, the amount of fine M₂C carbides was greatly increased, while that of coarse M₃C carbides was decreased, thereby leading to the improvement of tensile properties and impact toughness. Their simulated HAZs also had sufficient impact toughness after postweld heat treatment (PWHT). These findings suggested that the low-alloy steels with high strength and toughness could be processed by decreasing carbon and manganese contents and by increasing molybdenum content.     

Upgrading the microstructure and the mechanical properties of cast high speed steel

The main problem of near‐net‐shape cast high speed steel toolings is the bad toughness due to the presence of relatively coarse structure and eutectic brittle carbide network. To overcome this problem intensive secondary cooling in oil immediately after casting was achieved, however special standard tool steels with high amount of austenite stabilizing elements were selected to give austenite + carbide in as‐cast condition. This eliminates the risk of martensitic transformation during intensive secondary cooling. Prespherodisation heat treatment at different temperatures was applied to improve the carbide morphology in cast structures of these steels. This is because traditional hardening of high speed (TS‐1 and TS‐2) cast steels showed severe deterioration in carbide morphology and increased noncoherency with the matrix. In this case, skeleton brittle carbide morphologies were detected in such steels. Impact toughness of prespherodised hardened high speed cast steel (TS‐2) was more or less higher than that of the normally heat treated steel, especially at section sizes lower than 20 mm. Meanwhile the prespherodised steel showed lower toughness at section sizes of more than 20 mm. The hot hardness for the same thickness and test temperature of normally hardened high speed steels was higher to some extent than that for prespherodised and hardened ones. However, the hot hardness increases as the size of sample increases, due to the gross of eutectic and secondary carbide.