Thermal Stability in Nanocrystalline Fe-30?Wt?Pct Ni Alloy Induced by Surface Mechanical Attrition Treatment

By means of surface mechanical attrition treatment (SMAT), a nanocrystalline surface layer is produced in Fe-30 wt pct Ni alloy, accompanying the formation of the strain-induced martensite. The thermal stability of nanocrystalline martensite and parent phase austenite in Fe-30 wt pct Ni alloy is studied by X-ray diffraction (XRD) and transmission electron microscope (TEM). The grain growth kinetics parameters, time exponent, n, and activation energy, Q, for both martensite and austenite, are determined, respectively. The TEM observations indicate that abnormal grain growth occurs during annealing at high temperatures.     

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     

Martensitic transformations induced by plastic deformation in the Fe-Ni-Cr-C system

Martensitic transformations induced by plastic deformation are studied comparatively in various alloys of three types: Fe-30 pct Ni, Fe-20 pct Ni-7 pct Cr, and Fe-16 pet Cr-13 pct Ni, with carbon content up to 0.3 pct. For all these alloys the tensile properties vary rapidly with temperature, but there are large differences in the value of the temperature rangeM _s toM _d, which strongly increases with substitution of chromium for nickel or with carbon addition. Using the node method, it is found that the intrinsic stacking fault energy in the austenite drastically increases with temperature in all the chromium-bearing alloys investigated. This variation is consistent with the observed influence of temperature on the appearance of twinning or ε martensite during plastic deformation. Very different α’ martensite morphologies can result from spontaneous and plastic deformation induced transformations, especially in Fe-20 pct Ni-7 pct Cr-type alloys where platelike and lath martensites are respectively observed. As in the case of ε martensite, the nucleation process is analyzed as a deformation mode of the material, using a dislocation model. It is then possible to account for the morphology of plastic deformation induced α’ martensite in both Fe-20 pct Ni-7 pct Cr and Fe-16 pct Cr-13 pct Ni types alloys and for the largeM _s toM _d range in these alloys. This paper is based upon a thesis submitted by F. LECROISEY in partial fulfillment of the degree of Doctor of Philosophy at the University of Nancy.     

The triggering mechanism of the martensitic transformation

The martensitic transformation involves, at least partly, a shear deformation of the parent lattice. Because the assumption that the martensitic transformation represents a macroscopic shear instability of the parent solid is at variance with experimental observations, the shear instabilities must be microscopic in nature. A model based on the dynamics of a dislocation stacking fault configuration (DSFC) adequately describes previous data as well as our own observations of a sharp decrease of the elastic constants of a Fe-28 wt pct Ni alloy just prior to the onset of the transformation. In terms of this model, theM _s temperature represents the temperature at which the dislocation stacking fault configuration becomes thermodynamically unstable. In terms of the present harmonic approximation, the unhindered expansion of the DSFC will therefore trigger the martensitic transformation. TETSURO SUZUKI, formerly with the University of Missouri-Rolla, Rolla, Missouri     

Some Effects of Parent Phase Aging on the Martensitic Transformation in a Cu- AI- Ni Shape Memory Alloy

Transmission electron microscopy observations have been carried out for a Cu-14 pct Al-4 pct Ni (wt pct) alloy aged in the thin foil state in an electron microscope. It was found that large cuboidal precipitates of theγ ₂ phase and many small domains of a highly ordered phase form in the DO₃ matrix during aging. The small ordered domains form preferentially on matrix antiphase boundaries as well as within the antiphase domains. The formation ofγ ₂ and the highly ordered phase, both of which are rich in alloy content, depletes the matrix of solute and thus raises the transformation temperaturesM _s andM _f. The small domains of the highly ordered phase prevent the propagation and reversion of martensite plates, leading to higherM _s-M_f andA _fins-A_f temperature intervals.     

Substructure of ausformed martensite in Fe-Ni and Fe-Ni-C alloys

The martensite substructure after ausforming has been studied for two different martensite morphologies: partially twinned, lenticular martensite (Fe-33 pct Ni, M_s =-105?C) and completely twinned “thin plate” martensite (Fe-31 pct Ni-0.23 pct C, M_s = -170?C), and in both cases ausforming produces a dislocation cell structure in the austenite which is inherited, without modification, by the martensite. In the Fe-Ni alloy, the dislocation cell structure is found in both the twinned (near the midrib) and untwinned (near the interface) regions, the latter also containing a regular dislocation network generated by the transformation itself and which is unaltered by the austenite dislocation cell structure. Similarly, in the Fe-Ni-C alloy, the transformation twins are unimpeded by the prior cell structure. These observations show that carbide precipitation during ausforming is not necessarily required to pin the austenite cell structure and that the martensite-austenite interface, backed by either twins or dislocations, does not exhibit a ”sweeping” effect. Although the martensite transformation twins are not inhibited by the ausforming cell structure, they do undergo a refinement with increased ausforming, and it is indicated that the transformation twin width in martensite depends on the austenite hardness. However, the relative twin widths remain unchanged, as expected from the crystallographic theory.     

Shear localization-martensitic transformation interactions in Fe-Cr-Ni monocrystal

A Fe-15 wt pct Cr-15 wt pct Ni alloy monocrystal was deformed dynamically (strain rate ∼10⁴ s⁻¹) by the collapse of an explosively driven thick-walled cylinder under prescribed initial temperature and strain conditions. The experiments were carried out under the following conditions: (a) alloy in austenitic state, temperature above transformation temperature; (b) alloy in transformed state; and (c) alloy at temperature slightly above M _s , propitiating concurrent shear-band propagation and martensitic transformation. The alloy exhibited profuse shear-band formation, which was a sensitive function of the deformation condition. Stress-assisted and strain-induced martensitic transformation competes with shear localization. The alloy deformed at a temperature slightly above M _s shows a significantly reduced number of shear bands. The anisotropy of plastic deformation determines the evolution of strains and distribution of shear bands. The different conditions showed significant differences that are interpreted in terms of the microstructural anisotropy. Calculated shear-band spacings based on the Grady-Kipp (GK) and Wright-Ockendon (WO) theories are compared with the observed values. The microstructure within the shear bands was characterized by transmission electron microscopy. Regions of sub-micron grain sizes exhibiting evidence of recrystallization were observed, as well as amorphous regions possibly resulting from melting and rapid resolidification. This article is based on a presentation given in the symposium “Dynamic Deformation: Constitutive Modeling, Grain Size, and Other Effects: In Honor of Prof. Ronald W. Armstrong,” March 2–6, 2003, at the 2003 TMS/ASM Annual Meeting, San Diego, California, under the auspices of the TMS/ASM Joint Mechanical Behavior of Materials Committee.     

Influence of strain-induced martensitic transformations on fatigue crack growth rates in stainless steels

The fatigue crack growth rates (FCGR) of two unstable austenitic stainless steels (Fe-16 Cr-13Ni) and (Fe-18Cr-6.5Ni-0.19C) were determined in theM_s-M_d temperature range where a strain induced μ → α′ martensitic transformation occurs near the crack tip. These FCGR were compared to the rates measured in the stable austenitic phase of a Fe-31.5Ni and a Fe-34 Ni alloy and in the martensitic phase obtained by quenching the Fe-31.5 Ni alloy below M_s. In the Fe-31.5 Ni, the FCGR are an order of magnitude higher in the martensitic than in the austenitic structures for ΔK ≤ 40 ksi in. The FCGR of the stainless steels decrease markedly when the test temperature approachesM _s in theM _s - M_d range. The FCGR for the alloy Fe-18Cr-6.5 Ni-0.19 C in a warm-worked condition are consistently higher than for the same alloy in the annealed condition for ΔK ≤ 40 ksi √in.. The results are discussed in terms of the influence of phase structures, stacking fault energy and work hardening exponent on the FCGR.     

Substructure of ausformed martensite in Fe-Ni and Fe-Ni-C alloys

The martensite substructure after ausforming has been studied for two different martensite morphologies: partially twinned, lenticular martensite (Fe-33 pct Ni, M_s =-105‡C) and completely twinned “thin plate” martensite (Fe-31 pct Ni-0.23 pct C, M_s = -170‡C), and in both cases ausforming produces a dislocation cell structure in the austenite which is inherited, without modification, by the martensite. In the Fe-Ni alloy, the dislocation cell structure is found in both the twinned (near the midrib) and untwinned (near the interface) regions, the latter also containing a regular dislocation network generated by the transformation itself and which is unaltered by the austenite dislocation cell structure. Similarly, in the Fe-Ni-C alloy, the transformation twins are unimpeded by the prior cell structure. These observations show that carbide precipitation during ausforming is not necessarily required to pin the austenite cell structure and that the martensite-austenite interface, backed by either twins or dislocations, does not exhibit a ”sweeping” effect. Although the martensite transformation twins are not inhibited by the ausforming cell structure, they do undergo a refinement with increased ausforming, and it is indicated that the transformation twin width in martensite depends on the austenite hardness. However, the relative twin widths remain unchanged, as expected from the crystallographic theory. T. MAKI, Formerly with the University of Illinois     

An investigation of the effects of austenite strength and austenite stacking fault energy on the morphology of martensite in Fe-Ni-Cr-0.3C alloys

The relative effects of austenite stacking fault energy and austenite yield strength on martensite morphology have been investigated in a series of three Fe-Ni-Cr-C alloys. Carbon content (0.3 wt pct) andM ₆ temperature (− 15°) were held constant within the series. Austenite yield strength atM _s was measured by extrapolating elevated temperature tensile data. Austenite stacking fault energy was measured by the dislocation node technique. Martensite morphologies were characterized by transmission electron microscopy and electron diffraction techniques. A transition from plate to lath martensite occurred with decreasing austenite stacking fault energy. The austenite yield strength atM _s for the low SFE, lath-forming alloy was found to be higher than previously reported for lath-forming alloys. The relative effects of these variables on martensite morphologies in these alloys is discussed.     

Transformation squence in a Cu-Al-Ni shape memory alloy at elevated temperatures

Precipitation sequences in a Cu-14 pct Al-4 pct Ni (wt pct) shape memory alloy were studied by means of transmission electron diffraction and microscopy as well as X-ray microanalysis techniques. On aging thin foil specimens up to 550 °C in the electron microscope, an as-quenched sample having a mixture of 2H-type and D0₃-type metastable structures transformed to the stable simple cubic γ₂ phase at or above 450 °C. The remaining matrix either showed precipitates of the fcc α-phase on prolonged annealing at 500 to 550 °C for a longer period, or transformed to martensite on cooling below theM _s temperature (~150 °C).     

Relationship between austenite dislocation density introduced during thermal cycling and M s temperature in an Fe-17 wt pct Mn alloy

The reason why thermal cycling decreases the martensite start (M _s ) temperature of an Fe-17 wt pct Mn alloy was quantitatively investigated, based on the nucleation model of ε martensite and a thermodynamic model for a martensitic transformation. The M _s temperature decreased by about 22 K after nine cycles between 303 and 573 K, due to the increase in shear-strain energy (ΔG _sh ) required to advance the transformation dislocations through dislocation forests formed in austenite during thermal cycling. The ΔG _sh value increased from 19.3 to 28.8 MJ/m³ due to the increase in austenite dislocation density from 1.5 × 10¹² to 3.8 × 10¹³/m² with the number of thermal cycles (in this case, up to nine cycles). The austenite dislocation density increased rapidly for up to five thermal cycles and then increased gradually with further thermal cycles, showing a good agreement with the increase in austenite hardness with the number of thermal cycles.     

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.     

Evolution of Slip Morphology and Fatigue Crack Initiation in Surface Grains of Ni200

The evolution of slipbands into fatigue cracks in surface grains of commercially pure Ni, Ni200 (99.35Ni-0.4Fe-0.25Cu, in wt pct), was studied at ambient temperature. Round-bar specimens with electropolished surfaces were fatigued under displacement-controlled, fully reversed conditions at four strain amplitudes under a nominal strain rate of 1 × 10⁻³ s⁻¹. Low-cycle fatigue tests were periodically interrupted to characterize the slip morphology at various fatigue cycles using scanning electron microscopy. The results showed that the distribution of slip in Ni200 varied considerably in individual surface grains at a given strain amplitude. Some grains were deformed more severely and exhibited more intense slipbands than others, while some surface grains showed the absence of slip lines with no evidence of plastic deformation. The evolutions of slipband width and spacing in deformed surface grains were followed as a function of fatigue cycles in order to assess the slipband morphology at the onset of fatigue crack initiation.     

Thermodynamics of carbon in austenite and Fe-Mo austenite

A Cahn Electrobalance has been used to determine directly and very accurately the carbon content of iron, iron-0.48 wt pct molybdenum and iron-1.16 wt pct molybdenum specimens which were equilibrated with a series of methane-hydrogen gas mixtures of constant composition. The equilibria investigated involved the austenite phases of the alloys at 783, 813 and 848‡C. The experimental results permit direct calculation of the activities of carbon in the samples, relative to graphite as unity, and of the enthalpy and entropy of solution of carbon. The results are compared with the experimental measurements of a number of other investigators. The results are in excellent agreement with those of Smith and Schenck and Kaiser for the Fe-C system at 800‡C, and indicate -H _C ^/M values of 9700 ± 500 cal/mole for pure Fe, 10,030 ± 500 cal/mole for an Fe-0.48 wt pct Mo alloy, and 10,150 ± 500 cal/mole for an Fe-1.16 wt pct Mo alloy. The effect of molybdenum in austenite is to decrease the activity coefficient of carbon in austenite.     

Effects of thermal cycling on the kinetics of the γ → ε martensitic transformation in an Fe-17 wt pct Mn alloy

The thermal cycling of an Fe-17 wt pct Mn alloy between 303 and 573 K was performed to investigate the effects of thermal cycling on the kinetics of the γ → ε martensitic transformation in detail and to explain the previous, contrasting results of the change in the amount of ε martensite at room temperature with thermal cycling. It was observed that the shape of the γ → ε martensitic transformation curve (volume fraction vs temperature) changed gradually from a C to an S curve with an increasing number of thermal cycles. The amount of ε martensite of an Fe-17 wt pct Mn alloy at room temperature increased with thermal cycling, in spite of the decrease in the martensitic start (M _s) temperature. This is due to the increase in transformation kinetics of ε martensite at numerous nucleation sites introduced in the austenite during thermal cycling.     

Thermodynamics of carbon in austenite and Fe-Mo austenite

A Cahn Electrobalance has been used to determine directly and very accurately the carbon content of iron, iron-0.48 wt pct molybdenum and iron-1.16 wt pct molybdenum specimens which were equilibrated with a series of methane-hydrogen gas mixtures of constant composition. The equilibria investigated involved the austenite phases of the alloys at 783, 813 and 848‡C. The experimental results permit direct calculation of the activities of carbon in the samples, relative to graphite as unity, and of the enthalpy and entropy of solution of carbon. The results are compared with the experimental measurements of a number of other investigators. The results are in excellent agreement with those of Smith and Schenck and Kaiser for the Fe-C system at 800‡C, and indicate -H _C ^/M values of 9700 ± 500 cal/mole for pure Fe, 10,030 ± 500 cal/mole for an Fe-0.48 wt pct Mo alloy, and 10,150 ± 500 cal/mole for an Fe-1.16 wt pct Mo alloy. The effect of molybdenum in austenite is to decrease the activity coefficient of carbon in austenite.     

Magnetic investigation of the effect of small additions of cobalt and manganese on the martensite reversal in an Fe-Ni alloy

Data on the temperature and composition dependence of the magnetic moment and Curie temperature of several Fe-Ni-Co and Fe-Ni-Mn alloys have been obtained. The temperature dependence of the magnetization was obtained for each alloy from 298 to 873 K, following the magnetization change through the transformation from martensite to austenite. The effect of cobalt and manganese additions to an Fe-29.9 at. pct Ni alloy on the reverse transition temperature,A _s , the Curie temperature,T _c , and the saturation magnetization at absolute zero, ρ_so, has been determined, Values forA _s , T _c , and ρ_so were obtained by fitting a Brillouin function to the respective contributions of austenite and martensite to the total magnetization. This technique represents a very sensitive method of obtaining transition temperatures and the respective amounts of each phase present in the alloys. A theoretical prediction of ρ_so andT _c was in agreement with the experimentally determined values.     

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.