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.     

The effect of Na2O on dephosphorization by CaO-based steelmaking slags

The effect of Na₂O on the equilibrium phosphorous distribution ratio between slag and iron or iron alloys, L_P, has been measured for CaO-SiO₂, CaO-FeOr-SiO₂ (CaO or 2CaO·SiO₂ saturated), and CaO-Al₂-SiO₂ slags. The addition of Na₂O to CaO-SiO₂ slags significantly increases L_P and the phosphate capacity. A 25 pct CaO-25 pct Na₂O-SiO₂ slag has a distribution ratio nearly two orders of magnitude greater than a comparable binary 50 pct CaO-SiO₂ slag. For the CaO-saturated slags containing 40 wt pct FeO_T, the addition of 6 wt pct Na₂O increases L_P by a factor of 5. For the 2CaO·SiO₂-saturated CaO-FeO_T-SiO₂ slag, there is an optimum FeOr content (20 wt pct) for dephosphorization, and 10 wt pct Na₂O increases L_P by a factor of 2. For reducing slags typically used in ladle metallurgy for Al-killed steels (50 pct CaO-40 pct Al₂O₃-10 pct SiO₂), as little as 3 wt pct Na₂O increases L_P by a factor of 100. The present results indicate that small additions of Na₂O to conventional steelmaking slags can greatly improve dephosphorization. Formerly Graduate Student, Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University.     

Effects of vanadium and processing parameters on the structures and properties of a direct-quenched low-carbon Mo-B steel

The structures and mechanical properties of a series of thermomechanically processed, direct-quenched martensitic 0.1C-1.4Mn-0.5Mo-B steels containing from 0 to 0.24 wt pct va have been investigated and compared to those obtained after a conventional austenitizing-and-quenching treatment. For all processing conditions, vanadium additions to the base composition are found to increase hardenability (ideal critical parameter,D,); the largest effects (up to a 90 pct increase inD _I) are noted when samples are hot-rolled prior to direct quenching. Vanadium additions are also observed to provide significant strengthening in the quenched-and-tempered condition as the result of the precipitation of fine V-Mo carbides. The strengthening increment due to these precipitates is approximately 100 MPa/0.1 wt pct V over the range of vanadium additions examined. At the same time, however, these precipitates reduce notch toughness; on the average, the 20 J transition temperature increases by about 4 °C for each 10 MPa increment in yield strength. For the conditions examined, the best balance of strength and toughness is obtained in direct-quenched samples which are control-rolled(i.e., rolling is completed below the austenite recrystallization temperature) prior to quenching.     

Activities of boron in the binary Ni-B and the ternary Co-Fe-B melts

Activities of boron in the binary Ni-B and the ternary Co-Fe-B melts have been directly determined by the electromotive force (emf) measurement. A boron crystal was mainly used as the reference electrode, and a ternary 29 wt pct B₂O₃-42 wt pct CaO-29 wt pct Al₂O₃ oxide melt was used as the electrolyte. Large negative deviations from Raoult’s law have been found in both the binary and the ternary systems. The activity of nickel has been calculated from the measured boron activity by means of the Gibbs-Duhem equation. Standard Gibbs energies of formation of Ni₃B (s), Fe₂B (s), and Co₃B (s) were estimated and compared with available data. Formerly Graduate Student, Department of Metallurgy, The University of Tokyo.     

Strength and toughness of Fe-10ni alloys containing C,Cr, Mo,and Co

The effects of C (0.10 to 0.20 pct), Cr (0 to 3 pct), Mo (0 to 2 pct), and Co (0 to 8 pct) on the yield strength, toughness (Charpy shelf energy), and tempering behavior of martensitic lONiCr-Mo-Co steels have been investigated. Variations in the carbon content between 0.10 and 0.20 pct result in yield strengths between 160 and 210 ksi (1.1 and 1.45 GN/m²) when these steels are tempered at 900° to 1000°F (480° to 540°C) for times of 1 to 100 h. These steels exhibit a secondary-hardening peak at 900° to 1000° F (480° to 540°C) where coarse Fe₃C carbides are gradually replaced by a fine, dislocation-nucleated dispersion of (Mo, Cr)₂C carbides. Maximum toughness at a given yield strength in these steels is only obtained when they are tempered for sufficiently long times so that the coarse Fe₃C carbides are completely dissolved. Molybdenum is primarily responsible for the secondary-hardening peak observed in these steels. However, chromium additions do result in lower secondaryhardening temperatures and promote coarsening of the secondary-hardening carbide. Best combinations of strength and toughness are obtained with steels containing 2 pct Cr and 1 pct Mo. Cobalt increases the yield strength of these steels over the entire tempering range and results in a higher secondary-hardening peak. This effect of cobalt is attributed to 1) a retardation in the rate of recovery of the dislocation substructure of the martensite, 2) the formation of a finer dispersion of secondary-hardening carbides, and 3) solid-solution strengthening. The finer dispersion of secondary-hardening carbides in steels containing cobalt is favored by the finer dislocation substructure in these steels since the (Mo, Cr)₂C carbide is dislocation-nucleated. This fine dispersion of (Mo, Cr)₂C carbide combined with the high nickel content accounts for the excellent combination of strength and toughness exhibited by these steels.     

Activities of boron in the binary Fe-B,Co-B,and Cu-B melts

Activities of boron in the binary Fe-B, Co-B, and Cu-B melts have been directly determined by the electromotive force (emf) measurement. Boron-saturated liquid Cu-B alloy was used as the reference electrode and a ternary 28 wt pct Al₂O₃-29 wt pct B₂O₃-43 wt pct CaO oxide melt was used as the electrolyte. Deviations of the boron activities from Raoult's law have been found largely negative for the Fe-B and Co-B systems but largely positive for the Cu-B system. Boron activities calculated from the literature data have not been in good agreement with the measured data. Activities of iron, cobalt, and copper have been calculated from the obtained boron activities by means of the Gibbs-Duhem equation. Some modifications to the liquidus curves on the Fe-B and Co-B phase diagrams have been presented. M. YUKINOBU, formerly Graduate Student, Department of Metallurgy, The University of Tokyo S. GOTO, Professor, formerly with the Department of Metallurgy, The University of Tokyo     

Retardation of intermetallic phase formation in experimental superferritic stainless steels

While superferritic stainless steels containing 29 pct chromium possess excellent resistance to corrosion, they may, under certain conditions, be embrittled by the precipitation of intermetallic phases. The extent to which the precipitation reactions can be retarded by alloying additions of aluminum and copper has been evaluated. It was found that additions of aluminum to an Fe-29 pct Cr-4 pct Mo-1.5 pct Ni base alloy suppress the precipitation of the undesirable sigma and chi intermetallic phases, but additions of up to 3 pct aluminum promote 475 ‡C embrittlement. Additions of copper slightly reduce the precipitation of sigma and chi phases under most conditions but enhance 475 ‡C embrittlement. The resistance to corrosion in 10 pct H₂SO₄ and 10 pct FeCl₃ was assessed. All the aluminum-containing alloys performed significantly better in H₂SO₄ than the base alloy; however, large additions of aluminum had a deleterious effect on the pitting resistance in FeCl₃. Additions of copper improved the resistance to FeCl₃ and lowered the rate of corrosion in the H₂SO₄ solution used.     

The effect of silicon and nickel additions on the sulfide spacing and fracture toughness of a 0.4 carbon low alloy steel

This paper discusses the effects of silicon and nickel additions on the mechanical properties of a 0.4 carbon low alloy steel. The four experimental steels used in the study were obtained by making additions of 1.5 wt pct nickel and 2 wt pct silicon, both separately and in combination, to a 0.4C/1.5Ni/1.0Cr/0.5Mn base steel. The base + Ni + Si steel, resulting from combined nickel and silicon additions, has a yield strength of 1682 MN/m² and impact and fracture toughnesses of 65 J and 115 MN/m^3/2, respectively. The other three steels have comparable strength levels but more typical impact and fracture toughnesses of about 30 J and 75 MN/m^3/2, respectively. The microstructures of the four steels are almost identical. The only significant observed difference among the four steels is that the sulfides in the base + Ni + Si steel are almost three times as large as those in the other three steels. As the four steels have similar sulfide volume fractions, there is a similar difference in sulfide spacings. The improved toughness of the base + Ni + Si steel is attributed to the increased sulfide spacing due to the influence of combined nickel and silicon additions on the average sulfide size.     

Effect of Carbon Reduction on the Toughness of 9CrWVTaN Steels

Nitride-strengthened, reduced activation, martensitic steel is anticipated to have higher creep strength because of the remarkable thermal stability of nitrides. Two nitride-strengthened, reduced activation martensitic steels with different carbon contents were prepared to investigate the microstructure and mechanical property changes with decreasing carbon content. It has been found that both steels had the microstructure of full martensite with fine nitrides dispersed homogeneously in the matrix and displayed extremely high strength but poor toughness. Compared with the steel with low carbon content (0.005 pct in wt pct), the steel with high carbon content (0.012 pct in wt pct) had not only the higher strength but also the higher impact toughness and grain coarsening temperature, which was related to the carbon content. On the one hand, carbon reduction led to Ta-rich inclusions; on the other hand, the grain grew larger when normalized at high temperature because of the absence of Ta carbonitrides, which would decrease impact toughness. The complicated Al₂O₃ inclusions in the two steels have been revealed to be responsible for the initiated cleavage fracture by acting as the critical cracks.     

Creep and creep rate curves of a 10cr-30mn austenitic steel during carbide precipitation

The effect of carbide precipitation on creep and creep rate curves was investigated for 10Cr-30Mn austenitic steel containing 0.003 to 0.55 wt pct carbon. After solution annealing, the specimens were subjected to creep testing at 873 K for up to 30 Ms (8300 hours). In the low-carbon steels containing below 0.1 wt pct carbon, where carbide precipitation scarcely occurred, the decrease in creep rate with time in the transient creep region was described by log έ = A - (1/3) log t, where A is a constant depending on stress and carbon concentration. On the other hand, in the high-carbon steels containing above 0.2 wt pct carbon, where extensive precipitation of M₂₃C₆ occurred, the creep rate decreased significantly at long times above 3 to 5 ks (1 hour), deviating from the preceding equation for the low-carbon steels. The Johnson-Mehl equation with the time exponent n = 2/3 provided a reasonable approximation for the significant decrease in creep rate at long times. This resulted from a stress-induced precipitation of M₂₃C₆ on dislocation lines produced by creep deformation. The rate constant of the Johnson-Mehl equation depended on carbon concentration but not on stress levels examined.     

The microstructural,mechanical, and fracture properties of austenitic stainless steel alloyed with gallium

The mechanical and fracture properties of austenitic stainless steels (SSs) alloyed with gallium require assessment in order to determine the likelihood of premature storage-container failure following Ga uptake. AISI 304 L SS was cast with 1, 3, 6, 9, and 12 wt pct Ga. Increased Ga concentration promoted duplex microstructure formation with the ferritic phase having a nearly identical composition to the austenitic phase. Room-temperature tests indicated that small additions of Ga (less than 3 wt pct) were beneficial to the mechanical behavior of 304 L SS but that 12 wt pct Ga resulted in a 95 pct loss in ductility. Small additions of Ga are beneficial to the cracking resistance of stainless steel. Elastic-plastic fracture mechanics analysis indicated that 3 wt pct Ga alloys showed the greatest resistance to crack initiation and propagation as measured by fatigue crack growth rate, fracture toughness, and tearing modulus. The 12 wt pct Ga alloys were least resistant to crack initiation and propagation and these alloys primarily failed by transgranular cleavage. It is hypothesized that Ga metal embrittlement is partially responsible for increased embrittlement.     

Influence of CaF<Subscript>2</Subscript> and Li<Subscript>2</Subscript>O on the Viscous Behavior of Calcium Silicate Melts Containing 12 wt pct Na<Subscript>2</Subscript>O

Understanding the viscous behavior of silica-based molten fluxes is essential in maintaining the reliability of steel casting operations and in preventing breakouts. In particular, high concentrations of aluminum in recently developed transformation induced plasticity (TRIP) and twinning induced plasticity (TWIP) steels tend to promote reduction of silica in the mold fluxes that result in the formation of alumina, which in turn increases the viscosity. To counteract this effect, significant amounts of fluidizers such as CaF₂ and Li₂O are required to ensure that mold fluxes have acceptable lubrication and heat transfer characteristics. The viscous behavior of the slag system based on CaO-SiO₂-12 wt pct Na₂O with various concentrations of CaF₂ and Li₂O has been studied using the rotating spindle method to understand the effects on the viscosity with these additives. CaF₂ additions up to 8 wt pct were effective in decreasing the viscosity by breaking the network structure of molten fluxes, but CaF₂ concentrations above this level had a negligible effect on viscosity. Li₂O additions up to 2 wt pct were also effective in decreasing the viscosity, but the effect was comparatively negligible above 2 wt pct. Using Fourier transform infrared (FTIR) analysis of as-quenched slag samples, it was concluded that the viscosity was controlled more effectively by changing the larger complex silicate structures of rings and chains than by changing the amounts of simpler dimers and monomers.     

Microstructure and phase identification in type 304 stainless steel-zirconium alloys

Stainless steel-zirconium alloys have been developed at Argonne National Laboratory to contain radioactive metal isotopes isolated from spent nuclear fuel. This article discusses the various phases that are formed in as-cast alloys of type 304 stainless steel and zirconium that contain up to 92 wt pct Zr. Microstructural characterization was performed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), and crystal structure information was obtained by X-ray diffraction. Type 304SS-Zr alloys with 5 and 10 wt pct Zr have a three-phase microstructure—austenite, ferrite, and the Laves intermetallic, Zr(Fe,Cr,Ni)_2+x. whereas alloys with 15, 20, and 30 wt pct Zr contain only two phases—ferrite and Zr(Fe,Cr,Ni)_2+x. Alloys with 45 to 67 wt pct Zr contain a mixture of Zr(Fe,Cr,Ni)_2+x and Zr₂(Ni,Fe), whereas alloys with 83 and 92 wt pct Zr contain three phases—α-Zr, Zr₂(Ni,Fe), and Zr(Fe,Cr,Ni)_2+x. Fe₃Zr-type and Zr₃Fe-type phases were not observed in the type 304SS-Zr alloys. The changes in alloy microstructure with zirconium content have been correlated to the Fe-Zr binary phase diagram.     

Effects of B,C, and Zr on the structure and properties of a P/M nickel base superalloy

The boron and carbon levels of a P/M nickel base superalloy were systematically varied in order to determine the mechanisms by which these elements strengthen the alloy, and their optimum concentration. Carbon levels were reduced to 20 ppm while the boron level was varied from 0.02 to 0.10 wt pct. Carbon levels of 0.002 and 0.05 wt pct were also studied, while maintaining a boron concentration of 0.02 wt pct. Zirconium levels were maintained at 0.06 wt pct. The resulting alloys were subjected to identical heat treatments and examinedvia SEM, TEM, and STEM microscopy. The alloys were also subjected to tensile, creep, stress-rupture, and fatigue crack growth tests. Results show that both carbon and boron have a strong influence on the formation of grain boundary precipitates, as expected. Carbon was present as the MC and M₂₃C₆ type carbides, while boron combined to form an intergranular M₃B₂ boride. Boron and zirconium were observed to be critical to the alloys' mechanical properties, although boron levels above the solubility limit resulted in no further improvement or debit in strength. Carbon additions resulted in no improvement in properties, indicating the feasibility of a carbon-free P/M superalloy. The role of the minor element additions is discussed in terms of both microstructural features and related strengthening mechanisms.     

Microstructure and mechanical properties of ductile Ni3AI-type compound in Fe-(Ni,Mn)-AI-C systems rapidly quenched from melts

By the rapid quenching technique, nonequilibrium Ni₃Al-type compounds with high strength and hardness as well as large elongation have been found in Fe-Ni-Al-C and Fe-Mn-Al-C systems. This formation region is limited to about 7 to 55 wt pct Ni, 3 to 9 wt pct Al and 0.8 to 2.4 wt pct C for Fe-Ni-Al-C and to about 7 to 65 wt pct Mn, 3 to 9 wt pct Al and 0.8 to 2.4 wt pct C for Fe-Mn-Al-C. The Ni₃Al-type compound has fine grains of about 1 to 10 μm in diam. Their Vickers hardness and yield strength increase with increase in the amounts of carbon, aluminum or nickel and the highest values attain about 665 DPN and 1690 MPa for Fe-Ni-Al-C and 600 DPN and 1740 MPa for Fe-Mn-Al-C. Elongation increases with decrease in carbon or aluminum and attains about 11 pct for Fe-20 wt pct Ni-6 wt pct Al-1.2 wt pct C and 28 pct for Fe-20 wt pct Mn-8 wt pct Al-1.6 wt pct C. The good strength and ductility of the Ni₃Al-type compounds remain unchanged on tempering for 1 h until heated to about 750 K. Further, it has been found that the addition of chromium, molybdenum or cobalt is effective for the improvement of mechanical properties and thermal stability of the compounds. Thus, the use of materials containing Ni₃Al-type compounds may be attractive for fine gage high-strength wire or plate applications. Formerly Graduate Student of Tohoku University.     

Optimization of mechanical properties of high-carbon pearlitic steels with Si and V additions

Systematic research has been undertaken on the effects of single and combined additions of vanadium and silicon on the mechanical properties of pearlitic steels being developed for wire rod production. Mechanical test results demonstrate that the alloy additions are beneficial to the mechanical properties of the steels, especially the tensile strength. Silicon strengthens pearlite mainly by solid-solution strengthening of the ferrite phase. Vanadium increases the strength of pearlite mainly by precipitation strengthening of the pearlitic ferrite. When added separately, these elements produce relatively greater strengthening at higher transformation temperatures. When added in combination the behavior is different, and substantial strength increments are produced at all transformation temperatures studied (550 °C to 650 °C). The addition of silicon and vanadium to very-high-carbon steels (>0.8 wt pct C) also suppresses the formation of a network of continuous grain-boundary cementite, so that these hypereutectoid materials have high strength coupled with adequate ductility for cold drawing. A wire-drawing trial showed that total drawing reductions in area of 90 pct could be obtained, leading to final tensile strengths of up to 2540 MPa in 3.3-mm-diameter wires.     

Growth parameters for aligned microstructures in directionally solidified aluminum-bismuth monotectic

Microstructures are shown for directionally solidified Al-3.4 wt pct Bi alloys with 0.2 wt pct Fe and 0.6 wt pct Fe additions. The third element causes the L_I/S_I + LII growth interface to become cellular. The bismuth forms at the cell nodes, appearing either as uniformly spaced arrays of spheres in the case of 0.2 wt pct Fe, or as an irregular net-work in the case of 0.6 wt pct Fe. Changes in the growth conditions which are known to control cellular structure are seen to have a similar effect on the bismuth spacing, with the cross sectional spacing varying as the inverse ofG (Temperature gradient) .R (Growth rate).     

Effect of alumina diluent on the fabrication of in-situ Al2O3-Ti/ZrB2 composite by self propagating high temperature synthesis dynamic compaction

A detailed investigation of the effect of alumina diluent on the Al₂O₃-TiB₂/ZrB₂ composite by self propagating high temperature synthesis (SHS) dynamic compaction was carried out. A dense composite could be obtained and microstructure could be tailored and controlled by adding alumina as diluent during the SHS reaction. The microhardness values decreased for 5 and 10 wt pct additions of alumna but increased for 15 and 20 wt pct additions. Hardness is influenced by the different phases present and the grain size.     

Influence of aluminum and chromium on the activity of oxygen in nickel based melts at 1600?C

The activity of oxygen in technically important nickel melts containing 15 wt pct cobalt and 5 wt pct molybdenum has been determined at 1600‡C for various concentrations of chromium ranging from 0 to 30 wt pct and aluminum varying from 0 to 15 wt pct. The activity of oxygen was measured by an electrochemical technique using yttria-doped thoria electrolyte cells. The results obtained are analyzed in terms of activity coefficients of oxygen as a function of aluminum and chromium contents in the melts. Clear positive deviations of the experimentally determined from the calculated activity coefficients of oxygen were found when aluminum was added to Ni-Co-Mo melts with or without chromium. From the results obtained in the range between 1 and 10 wt pct aluminum, the following equilibrium constants for the reaction 2 [Al] + 3 [O] ⇋ Al₂O₃ in the nickel based melts at 1600‡C were calculated: loga ₀ =-2/3 log [pct Al] - 3.94 for 0 pct Cr loga ₀ = -2/3 log [pct Al] - 4.21 for 10 pct Cr loga ₀ = -2/3 log [pct Al] - 4.81 for 20 pct Cr loga ₀ = -2/3 log [pct Al] - 5.06 for 30 pct Cr.