The role of thermal stabilization in martensite transformations

The variation of the kinetics of the martensite transformation with carbon content and martensite habit plane has been investigated in several Fe−Ni based alloys. Transformation in an Fe-25 wt pct Ni-0.02 wt pct C alloy exhibits predominantly athermal features, but some apparently isothermal transformation also occurs. In a decarburized alloy, on the other hand, the observed kinetic features, such as the dependence ofM _s on cooling rate, were characteristic of an isothermal transformation. In contrast, Fe-29.6 wt pct Ni-10.7 wt pct Co alloys with carbon contents of 0.009 wt pct C and 0.003 wt pct C transform by burst kinetics to {259}_γ plate. At both these carbon levels, theM _b temperatures of the Fe−Ni−Co alloys are independent of cooling rate. It is proposed that the change in kinetic behavior of the Fe-25 pct Ni alloy with the different carbon contents is due to the occurrence of dynamic thermal stabilization in the higher carbon alloy. Dynamic thermal stabilization is relatively unimportant in the Fe−Ni−Co alloys which transform by burst kinetics to {259}_γ plate martensite. P. J. FISHER, formerly with the University of New South Wales D. J. H. CORDEROY, formerly with the University of New South Wales     

Effects of copper on proeutectoid cementite precipitation

The effect of copper on proeutectoid cementite precipitation was investigated by examining the isothermal transformation characteristics of Fe-C and Fe-C-Cu alloys that had comparable carbon contents. The TTT diagrams generated for the Fe-1.43 wt pct C and the Fe-1.49 wt pct C-4.90 wt pct Cu alloys showed that the kinetics of proeutectoid cementite precipitation were not significantly affected by copper. The morphology of the proeutectoid cementite, as seen in the optical microscope, was also substantially the same in both alloys. However, transmission electron microscopy revealed the presence of small epsilon-copper precipitates within the proeutectoid cementite of the copper containing steel. It was concluded that this precipitation of ε-Cu took place at the cementite : austenite interphase boundaries, and that the transport of copper to the precipitates was accomplished by interphase boundary diffusion. The small influence of copper on the kinetics of proeutectoid cementite precipitation is discussed in terms of diffusional growth theories and the structure of the cementite : austenite interphase boundary.     

The effects of impurities and heat treatment on the internal friction of tungsten at high temperatures

An improved internal friction technique was used to study the relaxation processes in pure tungsten and the following alloys: commercially doped tungsten (218W), W-1 pct ThO₂, 218W-3 pct Re, and 218W-20 pct Re. Internal friction experiments were performed on worked and recrystallized specimens in the temperature range of 300° to 3000°K. The effects of impurities and alloying additions on the damping and recrystallization behavior of tungsten are demonstrated. It is further shown that the internal friction curves can conveniently be used to determine the temperature of primary and secondary recrystallization. The important effect of impurities on the microstructure and high temperature strength is also revealed by the temperature dependence of shear modulus.     

High Cycle Fatigue of (Fe,Ni, Co)3V type alloys

High cycle fatigue tests in vacuum have been performed on ordered (Fe, Co, Ni)₃V alloys between 25 °C and 850 °C. Heat-to-heat variations in fatigue properties of a Co-16.5 wtpct Fe-25 pct alloy, LRO-1, appeared to be due to differing quantities of grain boundary precipitates. Modification of this alloy with 0.4 pct Ti, to produce an alloy designated LRO-23, reduced the density of grain boundary precipitates and increased ductility, resulting in superior fatigue strength at high temperatures. The fatigue lives of LRO-1 and LRO-23 decreased rapidly above 650 °C, and increased intergranular failure was noted. The fatigue resistance of a cobalt-free alloy, Fe-29 pct Ni-22 pct V-0.4 pct Ti (LRO-37), was examined at 25 °C, 400 °C, and 600 °C; there was little evidence for intergranular fracture at any of these temperatures. Fatigue behavior of the LRO alloys is compared to that of conventional high temperature alloys.     

Effect of dissolved tungsten on the deformation of 70Ni-30Fe alloys

A series of Ni-Fe alloys containing various levels of tungsten in solid solution have been prepared as a means to assess the influence of solid solution strengthening on the mechanical behavior of monolithic 70Ni-30Fe. In particular, 70Ni-30Fe alloys plus equilibrium concentrations of tungsten in solid solution nominally correspond to the compositions associated with the matrix-only portion of certain tungsten heavy alloys, that is, alloys comprised of a high volume fraction of nominally pure tungsten particles embedded within a minority Ni-Fe-W based matrix. The study shows that the working solubility of tungsten within the 70Ni-30Fe base composition increases slightly with temperature, from approximately 21 wt pct at room temperature to approximately 23 wt pct at 1400 °C. Increasing the level of tungsten in solid solution leads to increases in room-temperature yield strength, tensile strength, and ductility. In contrast, the deformation characteristics of the alloys, as quantified by the power-law work-hardening exponent, n, and the strain-rate-sensitivity exponent, m, show little variation with tungsten solute concentration.     

Thermodynamics of inclusion formation in Fe-Cr-Ti-N alloys

The thermodynamics of titanium in Fe-Cr alloys and of inclusion formation in Fe-Cr-N-Ti alloys was investigated. A metal-nitride-gas equilibration technique was used to measure the activity of titanium. The equilibrium titanium content of the metal that is in equilibrium with pure solid titanium nitride and nitrogen gas at 1 atm was determined. The activity coefficients of titanium it(f_Ti) relative to 1 wt pct standard state in Fe were calculated for Fe-Cr alloys from the experimental results. The first-order interaction coefficient between titanium and chromium, e _Ti ^Cr , was determined to be 0.024 at 1873 K. The solubility of nitrogen in Fe-Cr alloys was measured and was found to increase with chromium content, which is in agreement with previous work. Thermodynamic calculations were made in order to predict under what conditions titanium nitride will form in 409 stainless steel and was compared with inclusions found in plant samples. The inclusion stability diagrams for 304 stainless steel and Fe-18 pct Cr and Fe-9 pct Cr alloys were computed.     

Gaseous oxygen absorption by molten iron and some Fe-AI,Fe-Si,Fe-Ti,and Fe-V alloys

An experimental investigation of the initial rates of oxygen dissolution in molten iron and some Fe-(≤9 pct Al), Fe-(≤6 pct Si), Fe-(≤1 pct Ti) and Fe-(≤1 pct V) alloys was carried out in pure oxygen. Two experimental techniques were employed in this study: a modified constant-volume Sieverts method and a falling droplet technique. It was found that the oxidation behavior of liquid iron-based alloys in gaseous pure oxygen as a function of alloy composition was similar under conditions of the falling droplet and modified constant volume Sieverts methods. Marked declines in the oxygen absorption rates were observed for Fe-Al and Fe-Si alloys when the initial alloy compositions reached 6 wt pct Al and 3 wt pct Si in iron, respectively. This behavior indicated a change in mode of oxidation from a burning to a passive type. Fe-Ti and Fe-V alloys initially containing up to 1 wt pct solute in iron exhibited only a burning type behavior. The sudden decline in oxygen absorption rate in molten iron-aluminum and iron-silicon alloys is discussed in terms of changes in the nature of the surface oxide film with increasing amounts of alloying element in the metal.     

The microstructure of chromium-tungsten steels

Chromium-tungsten steels are being developed to replace the Cr-Mo steels for fusion-reactor applications. Eight experimental steels were produced and examined by optical and electron microscopy. Chromium concentrations of 2.25, 5, 9 and 12 pct were used. Steels with these chromium compositions and with 2 pct W and 0.25 pct V were produced. To determine the effect of tungsten and vanadium, three other 2.25Cr steels were produced as follows: an alloy with 2 pct W and 0 pct V and alloys with 0 and 1 pct W and 0.25 pct V. A 9Cr steel containing 2 pct W, 0.25 pct V, and 0.07 pct Ta also was studied. For all alloys, carbon was maintained at 0.1 pct. Two pct tungsten was required in the 2.25Cr steels to produce 100 pct bainite (no polygonal ferrite). The 5Cr and 9Cr steels were 100 pct martensite, but the 12Cr steel contained about 25 pct delta-ferrite. Precipitate morphology and precipitate types varied, depending on the chromium content. For the 2.25Cr steels, M₃C and M₇C₃ were the primary precipitates; for the 9Cr and 12Cr steels, M₂₃C₆ was the primary precipitate. The 5Cr steel contained M₇C₃ and M₂₃C₆. All of the steels with vanadium also contained MC.     

Preparation and properties of some ODS Fe-Cr-Al alloys

Several alloys based on Fe-25Cr-6Al and Fe-25Cr-11Al (wt pct) with additions of yttrium, Al₂O₃, and Y₂O₃ have been prepared by mechanical alloying of elemental, master alloy and oxide powders. The powders were consolidated by extrusion at 1000°C with a reduction ratio of 36:1. The resulting oxide contents were all approximately either 3 vol pct or 8 vol pct of mixed Al₂O₃-Y₂O₃ oxides or of Al₂O₃. The alloys exhibited substantial ductility at 600°C: an alloy containing 3 vol pct oxide could be readily warm worked to sheet without intermediate annealing; an 8 vol pct alloy required intermediate annealing at 1100°C. The 3 vol pct alloys could be recrystallized to produce large elongated grains by isothermal annealing of as-extruded material at 1450°C, but the high temperature strength properties were not improved. However, these alloys, together with some of the 8 vol pct materials, could be more readily recrystallized after rod (or sheet) rolling; sub-stantially improved tensile and stress rupture properties were obtained following 9 pct rod rolling at 620°C and isothermal annealing for 2 h at 1350°C. In this condition, the rup-ture strengths of selected alloys at 1000 and 1100°C were superior to those of competitive nickel-and cobalt-base superalloys. The oxidation resistance of all the alloys was ex-cellent. F. G. WILSON and C. D. DESFORGES, formerly with Fulmer Re-search Institute     

An approach to developing an alternative hot work die steel

This paper evaluates an approach to developing a steel which combines resistance to softening on tempering with an economical use of alloy elements. To obtain the desired tempering behavior advantage has been taken of the ability of non-carbide forming elements to enhance the secondary hardening response and the tendency of vanadium additions to reduce the coarsening rate of Mo₂C. Five alloys were investigated; these were a base secondary hardening steel, that base steel modified by the addition of 2 wt pct silicon and by the combined addition of 1 wt pct silicon and 1 wt pct aluminum. To these two modified alloys were made additions of 0.4 wt pct vanadium. It was found that both types of additions without vanadium enhance the secondary hardening response to the same significant degree. Both of these alloys soften rapidly as the tempering temperature is increased above 600 °C. However, with the addition of vanadium, hardnesses over R_gC 50 are obtained after tempering at 650 °C. While silicon additions appear indispensable to this resistance to softening on tempering, silicon also favors the retention of primary carbides after austenitizing and, if present in sufficient amounts, can cause brittle intergranular fracture after tempering at high temperatures.     

Modulated structure and magnetic properties of age-hardenable Fe-Mn-Al-C alloys

Microstructural changes in the age-hardenable Fe-(30 to 34) wt pct Mn-(8 to 11) wt pct Al-(0.9 to 1.0) wt pct C alloys during aging in the temperature range between 773 and 823 K have been investigated by means of transmission electron microscopy (TEM) and X-ray diffraction. The wavelength of the modulated structure was found to be nearly constant for short aging times and then to increase on further aging, whereas the compositional modulation amplitude was found to increase rapidly from the beginning of aging. The growth of a spinodally modulated structure along the orthogonal «100» directions results in a periodic arrangement of the κ-carbide precipitates, (Fe, Mn)₃AlC_x, in the austenite matrix. The increases in hardness and residual and saturation inductions in the early stage of aging were in accord with the increase in the amplitude.     

The creep behavior of W-5 re

Polycrystalline W-5 wt pct Re was creep-tested in tension from 1500° to 1900°C at stresses from 2500 to 10,000 psi in a vacuum of 10^?8 torr. The steady-state strain rate was directly proportional to stress to the 5.5 power, and the apparent activation energy for creep was 104 kcal per mole. Dislocation substructure that developed during high-temperature deformation was studied by transmission electron microscopy. The total dislocation density was dependent on stress to the 2.1 power and was insensitive to temperature and strain. No subgrains were found in creep tested specimens. The rate-controlling deformation mechanism was ascribed to dislocation climb where the governing diffusion process was dislocation core diffusion. Comparison of creep data for tungsten, W-5 wt pct Re, and W-25 wt pct Re showed that W-5 wt pct Re alloy has significantly better creep properties than the other two materials.     

The effect of nitrogen on stacking fault energy of Fe-Ni-Cr-Mn steels

The effect of nitrogen content on stacking fault energy (SFE) has been measured in a series of Fe-21Cr-6Ni-9Mn alloys. Stacking fault energies were determined from node measurements using weak beam imaging techniques in transmission electron microscopy. Nitrogen additions lower the SFE from 53 mJ/m² at 0.21 wt pct to 33 mJ/m² at 0.24 wt pct. Further increases to 0.52 wt pct do not markedly change the SFE. Carbon and silicon had no effect on SFE in the ranges 0.010 to 0.060 wt pct C and 0.17 to 0.25 wt pct Si. The shift in SFE from 0.21 to 0.24 wt pct N is accompanied by a transition to a more planar plastic deformation mode. The sharp transition precludes the use of linear regression analysis for relating SFE to nitrogen content in this class of alloys.     

Interphase boundary precipitation in liquid phase sintered W-Ni-Fe and W-Ni-Cu alloys

The microstructure of liquid-phase sintered, tungsten-based heavy alloys comprises a continuous network of spheroidal tungsten single crystals embedded in a ductile, fcc matrix phase, and the integrity of the tungsten-matrix interphase boundaries established during processing is of major importance in determining the resultant mechanical properties. A serious potential source of embrittlement in these systems involves the precipitation of a brittle third phase along these boundaries. In the present work the techniques of selected area and convergent beam electron diffraction, energy dispersive X-ray microanalysis, and scanning Auger electron spectroscopy have been used to identify the embrittling interphase boundary precipitate formed in a commercial W-4.5 wt pct Ni-4.5 wt pct Fe alloy. The interphase boundary precipitation of an intermetallic phase in a W-7.2 wt pct Ni-2.4 wt pct Cu alloy under controlled conditions of heat treatment has also been confirmed. The precipitate phase observed in the W-Ni-Fe alloy in the as-sintered furnace-cooled condition has been found to be an eta carbide with a diamond cubic crystal structure (space group Fd3m,a ₀ = 1.092 ± 0.005 nm) and a tentative composition of the form (Ni,Fe)₆W₆C, where the Ni:Fe atom ratio is approximately 2:3. Neither the carbide nor any evidence of an intermetallic phase was observed in the as-sintered, furnace-cooled W-Ni-Cu alloy, but a continuous interphase boundary film of intermetallic precipitate could be induced in specimens solution treated at 1350°C, water quenched, and aged isothermally in the temperature range 600 to 900°C. Selected area electron diffraction indicated that the phase was isomorphous with the intermetallic Ni₄W of the binary Ni-W system. This paper is based on a presentation delivered at the symposium “Activated and Liquid Phase Sintering of Refractory Metals and Their Compounds” held at the annual meeting of the AIME in Atlanta, Georgia on March 9, 1983, under the sponsorship of the TMS Refractory Metals Committee of AIME. Formerly with Department of Mechanical and Industrial Engineering and Materials Research Laboratory, University of Illinois at Urbana-Champaign     

TEM Studies of Boron-Modified 17Cr-7Ni Precipitation-Hardenable Stainless Steel via Rapid Solidification Route

Commercial grade 17Cr-7Ni precipitation-hardenable stainless steel has been modified by adding boron in the range 0.45 to 1.8 wt pct and using the chill block melt-spinning technique of rapid solidification (RS). Application of RS has been found to increase the solid solubility of boron and hardness of 17Cr-7Ni precipitation-hardenable stainless steel. The hardness of the boron-modified rapidly solidified alloys has been found to increase up to ~280 pct after isochronal aging to peak hardness. A TEM study has been carried out to understand the aging behavior. The presence of M₂₃(B,C)₆ and M₂(B,C) borocarbides and epsilon-carbide in the matrix of austenite and ferrite with a change in heat treatment temperature has been observed. A new equation for Creq is also developed which includes the boron factor on ferrite phase stability. The study also emphasizes that aluminum only takes part in ferrite phase stabilization and remains in the solution.     

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.     

Nitrogen solubility in liquid Fe-V and Fe-Cr-Ni-V alloys

Nitrogen solubility in liquid Fe, Fe-V, Fe-Cr-V, Fe-Ni-V and Fe-18 pct Cr-8 pet Ni-V alloys has been measured using the Sieverts’ method for vanadium contents up to 15 wt pct and over the temperature range from 1775 to 2040 K. Nitrogen solution obeyed Sieverts’ law for all alloys investigated. Nitride formation was observed in Fe-13 pet V, Fe-15 pet V and Fe-18 pet Cr-8 pet Ni-10 pet V alloys at lower temperatures. The nitrogen solubility increases with increasing vanadium content and for a given composition decreases with increasing temperature. In Fe-V alloys, the nitrogen solubility at 1 atm N₂ pressure is 0.72 wt pet at 1863 K and 15 pct V. The heat and entropy of solution of nitrogen in Fe-V alloys were determined as functions of vanadium content. The first and second order interaction parameters were determined as functions of temperature as: $$e_N^V = \frac{{ - 463.6}}{T} + 0.148 and e_N^{VV} = \frac{{17.72}}{T} - 0.0069$$ The effects of alloying elements on the activity coefficient of nitrogen were measured in Fe-5 pet and 10 pet Cr-V, Fe-5 pet and 10 pet Ni-V and Fe-18 pet Cr-8 pct Ni-V alloys. In Fe-18 pet Cr-8 pet Ni-10 pet V, the nitrogen solubility at 1 atm N₂ pressure is 0.97 wt pet at 1873 K. The second order cross interaction parameters, e _N ^Cr,V and e _N ^Ni,V , were determined at 1873 K as 0.00129 and ? 0.00038 respectively.     

Structural Characterization of Sputter-Deposited 304 Stainless Steel+10 wt pct Al Coatings

An SS304?+?10?wt pct Al (with a nominal composition of Fe-18Cr-8Ni-10Al by wt pct and corresponding to Fe-17Cr-6Ni-17Al by at. pct) coating was deposited on a 304-type austenitic stainless steel (Fe-18Cr-8Ni by wt pct) substrate by the magnetron sputter-deposition technique using two targets: 304-type stainless steel (SS304) and Al. The as-deposited coatings were characterized by X-ray diffraction, transmission electron microscopy, and three-dimensional (3-D) atom probe techniques. The coating consists of columnar grains with ?? ferrite with the body-centered cubic (bcc) (A2) structure and precipitates with a B2 structure. It also has a deposition-induced layered structure with two alternative layers (of 3.2 nm wavelength): one rich in Fe and Cr, and the other enriched with Al and Ni. The layer with high Ni and Al contents has a B2 structure. Direct confirmation of the presence of B2 phase in the coating was obtained by electron diffraction and 3-D atom probe techniques.     

Studies of Carbides in a Rapidly Solidified High-Speed Steel

Rapid solidification by electron beam surface melting of a Mo-base high-speed steel (M7) has produced microstructural features different from those observed in the conventionally processed material. As a result of rapid solidification, the volume percent of the carbide phases formed has decreased sharply and has resulted in the formation of M₂C and M₂₃C₆ carbide phases, while in the conventionally processed material, M₆C and MC carbides were present. Microanalysis of the extracted carbides formed by electron beam melting has yielded an intriguing finding. M₂₃C₆ is found to be unusually rich in molybdenum, tungsten, and vanadium; the concentration of (Mo + W), for instance, is approximately 60 wt pct. The corresponding values for Fe and Cr are surprisingly low (6 wt pct Cr and 1 wt pct Fe). This is in marked contrast with carbides encountered in the conventionally processed high-speed steel, where Cr and Fe are the major constituents. The shift in composition of the carbide phases could be attributed to the accelerated evaporation of chromium during surface melting as compared to the evaporation of Mo, W, and V. formerly Research Associate, University of Connecticut     

Effects of tungsten content on the creep-rupture properties of low-carbon cobalt-base heat-resistant alloys

The effects of tungsten (W) content up to about 20 wt pct on the creep-rupture properties of low-carbon HAYNES 25-(L-605-) type cobalt-base alloys were investigated at 1089 and 1311 K. An increase in W content of about 5 wt pct resulted in tripling the rupture life without significant loss of creep ductility at 1311 K. The principal strengthening phases precipitated during creep at 1311 K were W solid solution and M₆C carbide precipitates in the matrix and on the grain boundaries. The amounts of these precipitates, especially precipitates of W solid solution, increased with increasing W content. The Cr₂₃C₆ carbide was also detected in those ruptured specimens of alloys containing more than 17 wt pct W. The creep ductility decreased a little, and the rupture life did not increase with increasing W content at 1089 K. Two types of carbides (Cr₂₃C₆ and M₆C), Co₂W (Laves phase), and α-Co were confirmed in the specimens ruptured at 1089 K. The amount of Co₂W harmful to ductility, as well as the amounts of strengthening phases (carbides), increased with increasing W content.