Observations of aging effects in a Cu-Sn shape memory alloy

A Cu-15.0 at. pct Sn alloy has been chosen as a model alloy for the study of aging effects in copper-based shape memory alloys. Different thermal aging treatments were carried out to determine the effects of both parent phase and martensite aging on the amount of shape recovery and the characteristic transformation temperaturesM _s ,A _s , andA _f . Aging of the martensite reduces both the amount of shape recovery and the extent of the reverse martensite → parent transformation. High martensite heating rates promote complete shape recovery and reverse transformation while the aging occurring during slow heating can inhibit or prohibit both. But irrespective of the martensite heating rate the transformation temperature hysteresis as given by (M _s -A _s ) is large for the Cu-15 pct Sn alloy compared to other shape memory alloys exhibiting thermoelastic behavior. On the other hand, some beneficial effects were noted when the Cu-15 pct Sn alloy was aged in the parent phase condition prior to subsequent transformation to martensite. TheM _s ,A _s , andA _f were lowered following prior parent phase aging, possibly because of a change in long range order, but prior parent phase aging was found to diminish the deleterious effect of martensite aging. Both shape recovery and the extent of the reverse martensite → parent transformation are enhanced by prior parent phase aging. The enhancement is greater the higher the aging temperature or the longer the aging time at a given temperature. J. D. STICE, formerly Research Assistant at 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.     

Ordering kinetics of Fe3Pt austenites and reversed austenites

Fe₃Pt austenites undergo an ordering reaction belowT _c in addition to the martensite transformation at a much lower temperature. It is to be expected that theM _s temperature will be affected by the degree of austenite order and the progress of austenite ordering can be conveniently represented by the variation ofM _s temperature. In this study it was found that heat treating the annealed austenites belowT _c , a single-stage ordering reaction which followed first order kinetics was observed. The ordering rate or the rate ofM _s temperature change was found to be composition dependent, faster for alloy closer to the stoichiometry. The reversed austenite contains transformation induced defect structure. Consequently, heat treating the reversed austenites belowT _c a two-stage reaction was observed. Annealing of defect structure was found to precede the ordering reaction. Both annealing and ordering followed first order kinetics. The salient feature during annealing was that the initial rate ofM _s temperature change appeared to be independent of alloy composition.     

Magnetic investigation of martensite ⇌ austenite transformations in Fe-Ni-Co alloys

The martensite ⇌ austenite transformations were investigated in Fe-Ni-Co alloys containing about 65 wt pct Fe and up to 15 wt pct Co. A change in morphology of martensite from plate-like to lath-type occurred with increasing cobalt content; this change in morphology correlates with the disappearance of the Invar anomaly in the austenite. The martensite-to-austenite reverse transformation differed depending on martensite morphology. Reversion of plate-like martensite was found to occur by simple disintegration of the martensite platelets. Reverse austenite formed from lath-type martensite was not retained when quenched from much aboveA _s, with microcracks forming during theM→γ→M transformation.     

Phase Equilibria and Phase Transition of the Ni–Fe–Ga Ferromagnetic Shape Memory Alloy System

Phase equilibria and martensitic and magnetic transitions of the β (B2 and L2₁) phase in the Ni–Fe–Ga system were investigated. The b phase was found to be in equilibrium with the γ (A1 structure) or γ′ (L1₂ structure) phase. The Curie temperature, T _c , equilibrium temperature, T _o 5 (Ms + Af)/2, martensitic transition starting temperature, M _s , and reverse transition finishing temperature, Af , of the β single–phase alloys were sensitive to the Fe and Ga compositions. The Fe substitution for Ni decreased and increased the T _o and T _c , respectively. The Ga substitution for Ni or Fe decreased both the T _o and T _c . The entropy change accompanying the reverse martensitic transition showed compositional dependence due to the magnetic contribution. The saturation magnetization I _s of the Ni–Fe–Ga system showed a strong dependence on the magnetic valence Z _M . The Is values of the Ni–Fe–Ga alloys annealed at 1023 K showed the same Z _m dependence as other ferromagnetic shape memory alloy (FSMA) systems. This article is based on a presentation made in the symposium entitled "Phase Transformations in Magnetic Materials," which occurred during the TMS Annual Meeting, March 12-16, 2006, in San Antonio, Texas, under the auspices of the Joint TMS–MPMD and ASMI–MSCTS Phase Transformations Committee.     

The effect of austenite ordering on the martensite transformation in Fe-Pt alloys near the composition Fe3Pt: I. Morphology and transformation characteristics

Fe-Pt alloys near the composition Fe₃Pt transform from fee austenite to bcc martensite at near ambient temperatures. The effect of austenite ordering in depressing theM _s temperature has been reported previously, but more importantly the present work shows that ordering leads to a reversible martensitic transformation. The characteristics of this reversible transformation have been investigated by optical metallography, cinematography, and electrical resistivity measurements. It is concluded that in austenite ordered to an appropriate degree, the transformation to martensite possesses all of the characteristics of a thermoelastic martensite transformation. This transformation in ordered Fe~25 at. pct Pt alloys is the first thermoelastic martensite transformation reported for an iron-base alloy. The present experiments indicate that martensite “nuclei” are not destroyed by the transformation, and are reactivated on each cooling cycle at approximately the same temperature. D. P. DUNNE, formerly with the University of Illinois at Urbana-Champaign, Urbana, 111. 61801     

The Effect of an Inert Oxide Particle Dispersion on the Morphology of Martensite in Fe-27Ni-0.025C Alloys

A series of dispersion strengthened Fe-Ni alloys has been prepared by powder metallurgical techniques. This series was designed to permit evaluation of the relative effects of M_s temperature, chemical driving force, and austenite yield strength on resultant martensite morphology without altering matrix chemistry. Using a carefully selected lath-forming Fe-27Ni-.025C base alloy, incremental additions of an inert oxide dispersion resulted in a decrease in M_s temperature, an increase in the thermodynamic driving force at M_s, and an increase in the austenite yield strength at M_s to values beyond those previously associated with the lath-to-plate morphology transition. As the M_s temperature dropped below about 0 °C, martensite morphology shifted from lath to an intermediate “twinned lath” to plate, while holding constant both matrix chemistry and thermal history. Previous correlations of thermodynamic driving force and austenite yield strength with martensite morphology have been shown to break down. It is concluded that the observed transition from lath to plate martensite in the present alloy series was induced primarily by the depression of M_s temperature into the plate-forming temperature regime of the Fe-Ni system.     

Influence of Manganese and Nickel on the α´ Martensite Transformation Temperatures of High Alloyed Cr‐Mn‐Ni Steels

The martensite start temperature (M_s), the martensite austenite re‐transformation start temperature (A_s) and the re‐transformation finish temperature (A_f) of six high alloyed Cr‐Mn‐Ni steels with varying Ni and Mn contents in the wrought and as‐cast state were studied. The aim of this investigation is the development of the relationships between the M_s, A_s, A_f, T₀ temperatures and the chemical composition of a new type of Cr‐Mn‐Ni steels. The investigations show that the M_s, A_s and A_f temperatures decrease with increasing nickel and manganese contents. The A_f temperature depends on the amount of martensite. Regression equations for the transformation temperatures are given. The experimental results are based on dilatometer tests and microstructure investigations.     

The effect of austenite prestrain above the Md temperature on the martensitic transformation in Fe-Ni-Cr-C alloys

The effect of austenite prestrain above theM _d temperature on the structure and transformation kinetics of the martensitic transformation observed on cooling was determined for a series of Fe-Ni-Cr-C alloys. The alloys exhibited a shift in martensite morphology in the nondeformed state from twinned plate to lath while theM _s temperature, carbon content, and austenite grain size were constant. The transformation behavior was observed over the temperature range 0 to -196°C as a function of tensile prestrains performed above theM _d temperature. A range of prestrains from 5 pct to 45 pct was investigated. It is concluded that the response of a given alloy to austenite prestrain above theM _d temperature can be correlated with the morphology of the martensite observed in the nondeformed, as-quenched state. For the range of prestrains investigated, the transformation of austenite to lath martensite is much more susceptible to stabilization by austenite prestrain above theM _d temperature than is the transformation of austenite to plate martensite.     

Austenite ferromagnetism and martensite morphology

The Curie temperature of the austenite, the martensite-start temperature, and martensite morphology have been determined in a series of nil-carbon Fe?Ni and Fe?Ni?Co alloys. For these alloys, austenite ferromagnetism aboveM _s is a necessary, but not sufficient, condition for the formation of lenticular rather than packet martensite. In contrast to Fe?Ni alloys where lenticular martensite only forms below ≈O°C, some of the Fe?Ni?Co alloys transform to this structure at temperatures up to ≈200°C. The results support the hypothesis that the resistance of austenite to plastic deformation affects the habit plane and thus morphology of the martensite which forms.     

The relationship between austenite strength and the transformation to martensite in Fe-10 pct Ni-0.6 pct C alloys

The effect of austenite yield strength on the transformation to martensite was investigated in Fe-10 pct Ni-0.6 pct C alloys. The strength of the austenite was varied by 1) additions of yttrium oxide particles to the base alloy and 2) changing the austenitizing temperature. The austenite strength was measured at three temperatures above theM _s temperature and the data extrapolated to the experimentally determinedM _s temperature. It is shown that the austenite yield strength is determined primarily by the austenite grain size and that the yttrium oxide additions influence the effect of austenitizing temperature on grain size. As the austenite yield strength increases, both theM _s temperature and the amount of transformation product at room temperature decrease. The effect of austenitizing temperature on the transformation is to determine the austenite grain size. The results are consistent with the proposal¹ that the energy required to overcome the resistance of the austenite to plastic deformation is a substantial portion of the non-chemical free energy or restraining force opposing the transformation to martensite.     

Effects of carbon content and ausaging on γ ↔ α′ transformation behavior and reverse-transformed structure in Fe-Ni-Co-Al-C alloys

The effects of carbon content and ausaging on austenite γ ↔ martensite (α′) transformation behavior and reverse-transformed structure were investigated in Fe-32Ni-12Co-4Al and Fe-(26,28)Ni-12Co-4Al-0.4C (wt pct) alloys. TheM _s temperature, the hardness of γ phase, and the tetragonality of α′ increase with increasing ausaging time, and these values are higher in the carbon-bearing alloys in most cases. The γ → α′ transformation behavior is similar to that of thermoelastic martensite; that is, the width of α′ plate increases with decreasing temperature in all alloys. The αt’ → γ reverse transformation temperature is lower in the carbon-bearing alloys, which means that the shape memory effect is improved by the addition of carbon. The maximum shape recovery of 84 pct is obtained in Fe-28Ni-12Co-4Al-0.4C alloy when the ausaged specimen is deformed at theM _s temperature and heated to 1120 K. There are two types of reverse-transformed austenites in the carbon-bearing alloy. One type is the reversed y containing many dislocations which were formed when the γ/α′ interface moved reversibly. The plane on which dislocations lie is (01 l)_γ if the twin plane is (112)_α′. The other type of reverse-transformed austenite exhibits γ islands nucleated within the α′ plates.     

Stress-Assisted and strain-induced martensites in FE-NI-C alloys

A metallographic study was made of the martensite formed during plastic straining of metastable, austenitic Fe-Ni-C alloys withM _s temperatures below 0°C. A comparison was made between this martensite and that formed during the deformation of two TRIP steels. In the Fe-Ni-C alloys two distinctly different types of martensite formed concurrently with plastic deformation. The large differences in morphology, distribution, temperature dependence, and other characteristics indicate that the two martensites form by different transformation mechanisms. The first type, stress-assisted martensite, is simply the same plate martensite that forms spontaneously belowM _s except that it is somewhat finer and less regularly shaped than that formed by a temperature drop alone. This difference is due to the stress-assisted martensite forming from cold-worked austenite. The second type, strain-induced martensite, formed along the slip bands of the austenite as sheaves of fine parallel laths less than 0.5μm wide strung out on the {111}_γ planes of the austenite. Electron diffraction indicated a Kurdjumov-Sachs orientation for the strain-induced martensite relative to the parent austenite. No stress-assisted, plate martensite formed in the TRIP steels; all of the martensite caused by deformation of the TRIP steels appeared identical to the strain-induced martensite of the Fe-Ni-C alloys. It is concluded that the transformation-induced ductility of the TRIP steels is a consequence of the formation of strain-induced martensite. Formerly a graduate student at Stanford University     

Ordering transformations and mechanical properties of Ti3Ai and Ti3Al-Nb alloys

Phase transformations and the kinetics of domain growth were studied in near stoichiometric Ti₃Al and in a similar alloy containing about 5 at. pct Nb (Cb). The alloys were quenched from the β and from the α+ β fields and were subsequently annealed in the α₂ field to study the ordering transformation. The critical temperature (T _c) for ordering was found to be between 1125 and 1150° for both alloys. When quenched from aboveT _c the microstructure of the stoichiometric compound contained massive martensite with small antiphase domains of average size 8 × 10^— μm. On annealing the quenched structures in the range 700 to 1000°, domain coalescence occurred, the domains growing approximately as the square root of the annealing time. The activation energy for the domain growth process was found to be 64.6 ± 6 Kcal/mole (2.68 ± 0.25 × 10⁵ J/mole). On quenching the alloy containing Nb the β transforms to a fine acicular martensite. On annealing, antiphase domain coalescence within the martensite plates and the simultaneous recrystallization of the martensite resulted in a fine subgrain structure even after annealing at 900° for up to 3 h. The mechanical properties and the fracture modes of the two alloys tested at 700° were correlated with the observed microstructural changes. The effects of Nb in this alloy are to slow the domain growth kinetics, to reduce the planarity of slip, and to increase nonbasal slip activity. Formerly NRC Research Associate in the Air Force Materials Laboratory, Wright-Patterson Air Force Base, OH     

The Effects of Composition and Aging on the Martensite and Magnetic Transformations in Ni-Fe-Ga Ferromagnetic Shape Memory Alloys

The martensite and magnetic transformations in Ni-Fe-Ga ferromagnetic shape memory alloys are very sensitive to both alloy chemistry and thermal history. A series of Ni-Fe-Ga alloys near the prototype Heusler composition (X₂YZ) were used to investigate how the martensite and magnetic transitions change with alloy composition and isothermal aging above and below the B2/L2₁ ordering temperature. Calorimetry and magnetometry were employed to measure the martensite transformation temperatures and Curie temperatures. Compositional variations of only a few atomic percent result in martensite start temperatures and Curie temperatures that differ by about 230 and 35 K, respectively. Aging a Ni₅₃Fe₁₉Ga₂₈ alloy for 3600 seconds at various temperatures shifts the martensite start temperature and the Curie temperature by almost 70 K. Transmission electron microscopy investigations were conducted on the aged Ni₅₃Fe₁₉Ga₂₈ alloy. The considerable variations in the martensite and magnetic transformations in these alloys are discussed in terms of microstructural differences resulting from alloy chemistry and aging treatments. This article is based on a presentation made in the symposium “Phase Transformations in Magnetic Materials: Magnetic Shape Memory Alloys which occurred March 14, 2006, during the TMS Spring Meeting in San Antonio, TX, under the auspices of the ASMI/MPMD-Phase Transformations, EMPMD/SMD-Chemistry & Physics of Materials, and EMPMDNanomaterials Committees."     

Shock-induced martensitic transformations in near-equiatomic NiTi alloys

Shock-impact generated tensile-stress pulses were used to induce B2-to-monoclinic martensitic transformations in two near-equiatomic NiTi alloys having different martensite transformation start (M _s ) temperatures. The NiTi-I alloy (M _s ≈+27 °C) impacted at room temperature at 2.0 and 2.7 GPa tensile stress-pulse magnitude, showed acicular martensite morphology. These martensite needles had a substructure containing microtwins, typical of “stress-assisted” martensite. The NiTi-II alloy (M _s ≈−45 °C) showed no martensite formation when shocked with tensile-stress pulses of 2 GPa. For tensile stresses of 4.1 GPa, the alloy showed spall initiation near the region of maximum tensile-stress duration. In addition, monoclinic martensite needles, with a well-defined dislocation substructure, typical of “strain-induced” martensite, were seen clustering around the spall region. No stress-assisted martensite was formed in this alloy due to its very low M _s temperature. The present article documents results of the use of a metallurgical technique for generating large-amplitude tensile stress pulses of finite duration for studies of phase transformations involving changes from a high density to a low density state.     

Martensite-to-austenite reverse transformation in Fe-Ni-Co alloys

The reverse martensitic transformation was investigated in three Fe-Ni-Co alloys containing acicular martensite by means of dilatometry and coercive force (H_c) measurements. Two maxima were observed in the H_c -T relationships: the first H_c peak occurred at the Curie temperature of the austenite and is attributable to magnetic effects in a material containing two ferromagnetic phases; the second H_c peak, with values near 400 oe, is caused by reverse transformation wherein the remaining ferromagnetic martensite has increased coercivity due to decreased particle size and increased shape anisotropy. Dilatometric measurements display a gradual decrease in expansivity in the early stages of reversal. This observation is explained by a two-step process for shear-type transformation in which the first austenite formed has high magnetostriction and low expansivity. As the magnetostriction is lost by further heating, a large expansion occurs which counteracts contraction due to the crystallographic phase change.     

Effect of heat and thermomechanical treatments on the linear thermal expansion coefficient of an N30K10T3 invar

The N30K10T3 invar that has a temperature of the onset of martensite transformation of austenite M _s ≈ −80°C and a Curie point θ_C ≈ 200°C after water-quenching from 1150°C is studied. The decomposition of a supersaturated solid solution is shown to substantially influence the linear thermal expansion coefficient. The alloy is studied in the following three initial states: after quenching, after phase transformation-induced hardening (γ → α_m → γ_p.h), and after cold (20°C) plastic deformation by 30%.     

Stabilization mechanisms of retained austenite in transformation-induced plasticity steel

Three stabilization mechanisms—the shortage of nuclei, the partitioning of alloying elements, and the fine grain size—of the remaining metastable austenite in transformation-induced plasticity (TRIP) steels have been studied by choosing a model alloy Fe-0.2C-1.5Mn-1.5Si. An examination of the nucleus density required for an athermal nucleation mechanism indicates that such a mechanism needs a nucleus density as large as 2.5 · 10¹⁷ m⁻³ when the dispersed austenite grain size is down to 1 μm. Whether the random nucleation on various heterogeneities is likely to dominate the reaction kinetics depends on the heterogeneous embryo density. Chemical stabilization due to the enrichment of carbon in the retained austenite is the most important operational mechanism for the austenite retention. Based on the analysis of 57 engineering steels and some systematic experimental results, an exponential equation describing the influence of carbon concentration on the martensite start (M _s) temperature has been determined to be M _s (K)=273+545.8 · e ^−1.362w _c(mass pct). A function describing the M _s temperature and the energy change of the system has been found, which has been used to study the influence of the grain size on the M _s temperature. The decrease in the grain size of the dispersed residual austenite gives rise to a significant decrease in the M _s temperature when the grain size is as small as 0.1 μm. It is concluded that the influence of the grain size of the retained austenite can become an important factor in decreasing the M _s temperature with respect to the TRIP steels.     

Martensitic and Magnetic Transformation Behaviors in Heusler-Type NiMnIn and NiCoMnIn Metamagnetic Shape Memory Alloys

Martensitic and magnetic transformation behaviors of Ni₅₀MnIn, Ni₄₅Co₅MnIn, and Ni_42.5Co_7.5MnIn Heusler alloys were investigated by differential scanning calorimetry (DSC), vibrating sample magnetometry (VSM), and transmission electron microscopy (TEM). The martensitic transformation starting temperature (M _s ) decreases with increasing In composition, while the Curie temperatures (T _c ) of the parent phase are almost independent in each alloy series. On the other hand, the addition of Co resulted in a decrease of the M _s and an increase of the T _c , and the degree of the decline of M _s was accelerated by magnetic transformation of the parent phase. The M _s temperature change induced by the magnetic field was also confirmed. It was found that the degree of M _s change is strongly related to the entropy change by the martensitic transformation, which shows a correlation with T _c -M _s . These behaviors can be qualitatively explained on the basis of thermodynamic considerations. This article is based on a presentation made in the symposium entitled “Phase Transformations in Magnetic Materials,” which occurred during the TMS Annual Meeting, March 12–16, 2006, in San Antonio, Texas, under the auspices of the Joint TMS-MPMD and ASMI-MSCTS Phase Transformations Committee.