Isothermal martensitic transformation in Fe-Ni and Fe-Ni-C alloys at subzero temperatures

A survey of experimental work on the isothermal martensitic transformation in the presence of prior martensite is given in Fe-Ni and Fe-Ni-C alloys having subzero Ms (Mb) temperatures. Low temperature dilatometric measurements are correlated with internal friction measurements in the 5 to 200 K temperature range. This study will show that this transformation can be discussed in terms ofC-curve behavior as in Fe-Ni-Mn alloys. Nevertheless, in Fe-Ni and Fe-Ni-C alloys internal stresses created by the austenite-to-martensite transformation during cooling play an important part in the development of the isothermal transformation. Furthermore, internal friction is shown to be proportional to expansivity thus indicating that the internal friction technique can be applied successfully for the study of phase transformations.     

Ni-Ga-Fe-Co铁磁形状记忆合金的磁性转变和马氏体相变

Ferromagnetic shape memory alloys (FSMAs) such as NiMnGa, FePd and FePt are attractive as a new magnetic actuator material. They show a large magnetic-field-induced strain of 3% - 9% due to the variant rearrangement. Recently, the present authors have reported that in the Ni-Ga-Fe alloy the martensitic transformationfrom the B2 and/or the L21 structures into a seven-layer or five-layer modulated structure occurs upon cooling. In this alloy system, however, it is impossible to obtain a martensite phase at RT with a Curie temperature (To) higher than 100℃. In this work, the effects of substitution of Co for Ni on the martensitic and magnetic transformations, crystal structures and phase equilibria in Ni-Ca-Fe alloys were studied. Ni-Ga-Fe-Co alloys were prepared by induction melting under an argon atmosphere. Small pieces of specimens were taken from the ingot and homogenized at 1433 K for 24 h followed by quenching in water. The obtained specimens were aged at 773 K for 24 h and then quenched. The compositions of each phase were determined by energy dispersion X-ray spectroscopy (El)X). The martensitic transformation temperatures and Tc were measured by differential scanning calorimetry (DSC) and vibrating sample magnetometer (VSM) measurement. The crystal structure of martensite phase was observed by X-ray diffractmeter (XRD) and transmission electron microscope (TEM). The Curie temperature Tc was increased with increasing Co content while the martensitic transformation temperature slightly decreased. In the Ni(54-x) Ga27 Fe19 Cox, Tc increases from 303 K to 408 K with increasing CO content from x=0 to x=6. The crystal structure of the martensite phase and the phase equiribria in the Ni-Fe-Ga-Co alloys will be also presented.     

The formation of Hcp and Bcc phases in austenitic iron alloys

The formation of the hcp (∈) and bcc (α) structures in pure iron under high pressure conditions, as well as the morphological and crystallographic aspects of martensitic transformation to these structures at atmospheric pressure in iron alloys, are reviewed., It is concluded that the unique features of α- or lath martensite formation are not dependent upon the presence of the ∈ phase. Application of the phenomenological theory of martensitic transformation has not successfully rationalized the crystallography of lath-martensite. The criterion for ∈- and α-phase formation is established using the regular solution approximation and appropriate lattice stability parameters. In particular, the ∈ phase can be formed in Fe?Ni?Cr compositions through stress-induced transformation attending α-martensite formation. Further consideration suggests that the ∈→α transformation is not expected at atmospheric pressure at temperatures below approximately 500°K in the alloys considered. Thus, two martensitic transformations, γ→∈ and γ→α, can occur jointly in certain alloys.     

Effect of Cobalt on Phase Formation, Microstructure, and Mechanical Properties of Cu50?xCoxZr50 (x?=?2, 5, 10, 20?at.?pct) Alloys

In this work, the effect of cobalt on the phase formation and mechanical properties of rapidly solidified Cu_50?xCo_xZr₅₀ (x?=?2, 5, 10, and 20?at.?pct) alloys was investigated. CuZr martensite forms in the case of low Co contents (x?=?2 and 5?at.?pct), while in the alloys with 10 and 20?at.?pct Co, the B2 phase is stable even at room temperature. The deformation behavior of the rods under compressive loading depends strongly on the microstructure and, thus, on the alloy composition. Cobalt affects the fracture strength of the as-cast samples, and deformation is accompanied by two yield stresses for high Co-content alloys, which undergo deformation-induced martensitic transformation.     

Co-Al二元系中的fcc/hcp马氏体相变和形状记忆效应

It is known that pure Co undergoes martensitic transformation from γ phase (fcc) to ε phase (hcp) by the movement of a/6<112> Shockley partial dislocations at around 400 ℃, however, there have been few systematic works on the SM effect in Co and Co-based alloys. In this study, the fcc/hcp martensitic transformation and the SM effect were investigated in Co-Al binary alloys(mole fraction of Al=0～16%).The γ/ε martensitic transformation temperatures were found from the DSC measurements to decrease with increasing Al content, while the transformation temperature hystereses were observed to increase from 60 ℃ at x(Al)=0 to 150 ℃at x(Al)= 16%. The SM effect evaluated by a conventional bending test was enhanced by the addition of Al over 4%(mole fraction) and Co-Al alloys containing over 10%(mole fraction) exhibit a good SM effect associated with the hcp →fcc reverse transformation above 200 ℃. The SM effect was significantly improved by precipitation ofβ (B2) phase and the maximal shape recovery strain of 2. 2% was obtained, which can be explained by precipitation hardening. The crystallographic orientations between theβ, ε and γ phases were also determined. Finally, the magnetic properties were investigated and it was found that the Curie temperature and saturation magnetization of Co-14% Al(mole fraction) are 690 ℃and 120 emu/g, respectively. It is concluded that the Co-Al alloys hold promise as new high-temperature and ferromagnetic SM alloys.     

添加Y2O3的ZrO2的等温和变温马氏体相变

The phase transformation from the high temperature tetragonal phase to the low temperature monoclinic phase of zirconia had been long considered to be a typical athermal martensitic transformation until it was recently identified to be a fast isothermal transformation. The isothermal nature becomes more apparent when a stabilizing oxide, such as yttria, is doped, by which the transformation temperature is reduced and accordingly the transformation rate becomes low.Thus it becomes easy to experimentally establish a C-curve nature in a TTT (Time-Temperature-Transformation) diagram. The C-curve approaches that of well known isothermal transformation of Y-TZP (Yttria Doped Tetragonal Zirconia Polycrystals), which typically contains 3mol% of Y2O3.In principle, an isothermal transformation can be suppressed by a rapid cooling so that the cooling curve avoids intersecting the C-curve in TTT diagram. Y-TZP is the case, where the stability of the metastable tetragonal phase is relatively high and thus the tetragonal phase persists even at the liquid nitrogen temperature. On the other hand, the high temperature tetragonal phase of pure zirconia can never be quenched-in at room temperature by a rapid cooling; instead it always turns into monoclinic phase at room temperature. This suggests the occurrence of an athermal transformation after escaping the isothermal transformation, provided the cooling rate was fast enough to suppress the isothermal transformation. Thus, with an intermediate yttria composition, it would be possible to obtain the tetragonal phase which is not only metastable at room temperature but athermally transforms into the monoclinic phase by subzero cooling.The objective of the present work is to show that, with a certain range of yttria content, the tetragonal phase can be quenched in at room temperature and undergoes isothermal transformation and athermal transformation depending on being heated at a moderate temperature or under-cooled below room temperature. Because both of the product phases are essentially the same monoclinic phase, both transformations are regarded as martensitic transformation, i. e. isothermal and athermal martensite. In some steels such as Fe-Mn-Ni and Fe-Ni-C, the occurrence of both isothermal and athermal martensitic transformations has been reported. However, in these cases, the isothermal transformation occurs at temperatures slightly above the Ms (Martensite start) temperatures, and thus these transformations are considered to conform the same C-curve. On the other hand, the Ms temperature of the present material is well below the C-curve, which suggests that completely different mechanisms are controlling the kinetics of these two modes of transformations. Other aspects on these transformations are also to be reported..     

Liquid separation effects in Fe−Cu alloys solidified under different cooling rates

The effect of cooling rates on the microstructure of Fe−Cu alloys was investigated. A variety of solidification techniques was employed, in order to obtain a wide range of cooling rates. At high cooling rates (about 10⁴ K/sec), and in the composition range 30 to 80 wt pct Cu, the microstructures showed clear evidence of metastable liquid separation. This indicates a melt supercooling of about 50 to 100 K. Liquid separation coupled with high interfacial velocities resulted in solute trapping, and in a spherical morphology for one of the solids. At cooling rates lower than 10⁴ K/sec no liquid separation was observed, and the alloys solidified in a conventional manner,i.e., with a polycrystalline or a dendritic microstructure, depending on the Cu content. The type of the γ-Fe to α-Fe solid state transformation, taking place during cooling after solidification, depends on the cooling rates as well as on the Cu content in the γ-Fe phase. At medium cooling rates the transformation is martensitic, while at low or high cooling rates a polycrystalline transformed structure is obtained. A. MUNITZ, formerly Visiting Research Associate at the University of Florida at Gainesville, FL 32611     

Comparison of shape memory characteristics of a Ti-50.9 At. Pct Ni alloy aged at 473 and 673 K

The effect of aging on transformation and deformation behavior, i.e., the transformation temperatures, shape memory behavior, and multistage martensitic and R-phase transformations, was investigated for a Ti-50.9 at. pct Ni alloy aged at a low temperature (<600 K) rarely used for practical applications and at a high temperature (>600 K) conventionally used for practical applications. It was found that there are many differences between aging at 473 and 673 K. The martensitic and R-phase transformation temperatures significantly varied depending on aging time and temperature. It is found that two-stage R-phase and multistage martensitic transformations appear in both the specimens aged at 473 and 673 K, respectively. The two-stage R-phase transformation appeared by aging at 473 K over 36 ks, while the multistage martensitic transformation (MSMT) appeared by aging at 673 K in the range of aging times between 1.2 and 36 ks. It is found that the critical stress for slip increases with increasing aging time in specimens aged at 473 K, while that of specimens aged at 673 K increases with increasing aging time until reaching a maximum, then it decreases with a further increase in aging time. It is also found that the critical stress for slip is superior for specimens aged at 473 K than that for specimens aged at 673 K. It was confirmed that dense and fine lenticular precipitates of about 10 nm in length were formed through aging, resulting in superior shape memory characteristics.     

Isothermal and athermal type martensitic transformations in yttria doped zirconia

The phase transformation from the high temperature tetragonal phase to the low temperature monoclinic phase of zirconia had been long considered to be a typical athermal martensitic transformation until it was recently identified to be a fast isothermal transformation. The isothermal nature becomes more apparent when a stabilizing oxide, such as yttria, is doped, by which the transformation temperature is reduced and accordingly the transformation rate becomes low.Thus it becomes easy to experimentally establish a C-curve nature in a TTT (Time-Temperature-Transformation) diagram. The C-curve approaches that of well known isothermal transformation of Y-TZP (Yttria Doped Tetragonal Zirconia Polycrystals), which typically contains 3mol% of Y2O3. In principle, an isothermal transformation can be suppressed by a rapid cooling so that the cooling curve avoids intersecting the C-curve in TTT diagram. Y-TZP is the case, where the stability of the metastable tetragonal phase is relatively high and thus the tetragonal phase persists even at the liquid nitrogen temperature. On the other hand, the high temperature tetragonal phase of pure zirconia can never be quenched-in at room temperature by a rapid cooling; instead it always turns into monoclinic phase at room temperature. This suggests the occurrence of an athermal transformation after escaping the isothermal transformation, provided the cooling rate was fast enough to suppress the isothermal transformation. Thus, with an intermediate yttria composition, it would be possible to obtain the tetragonal phase which is not only metastable at room temperature but athermally transforms into the monoclinic phase by subzero cooling. The objective of the present work is to show that, with a certain range of yttria content, the tetragonal phase can be quenched in at room temperature and undergoes isothermal transformation and athermal transformation depending on being heated at a moderate temperature or under-cooied below room temperature. Because both of the product phases are essentially the same monoclinic phase, both transformations are regarded as martensitic transformation, i. e. isothermal and athermal martensite. In some steels such as Fe-Mn-Ni and Fe-Ni-C, the occurrence of both isothermal and alhermal martensitic transformations has been reported. However, in these cases, the isothermal transformation occurs at temperatures slightly above the Ms (Martensite start) temperatures, and thus these transformations are considered to conform the same C-curve. On the other hand, the Ms temperature of the present material is well below the C-curve, which suggests that completely different mechanisms are controlling the kinetics of these two modes of transformations. Other aspects on these transformations are also to be reported..     

Isothermal martensite transformation in a 1.80 Wt Pct C steel

The linear products formed isothermally at 373 K in a 1.80 wt pct C steel (Ms = 346 K) were examined by means of transmission electron microscopy. They were first reported as “black line products” by Greninger and Troiano. The isothermal product was of a thin plate with about 0.5 μm width, and it contained {112}_b transformation twins and revealed a habit plane of {3 15 10}_f. The orientation relationship between austenite and product was close to the Nishiyama relationship. These crystallographic data were in good agreement with those calculated by the phenomenological theory of martensitic transformation. Consequently, the product was determined not to be lower bainite, but isothermal martensite. The black color of isothermal martensites resulted from the fact that they were easily etched by the precipitates of epsilon carbide formed during the isothermal holding.     

FCC → FCT martensitic transformation in two-phase Mn–Cu alloys

The fcc → fct martensitic transformation in Mn–Cu alloys, which contain two isomorphous fcc phases with different manganese contents, is considered. The influence of the ratio of contents of these phases, the phase dispersity, and the state of interphase boundaries on the development of the martensitic transformation in the volume of the alloys is described. As a result of these factors, the martensitic transformation can cover the entire volume of an alloy, including particles with the manganese content that is lower than the critical content required for the martensitic transformation to occur in single-phase solid solutions, and can take place only in manganese-rich particles. In the first case, a general tetragonal structure modulated with respect to lattice parameter c forms in the volume of a two-phase alloy.     

Discontinuous precipitation and coarsening in Al-Zn alloys

The morphology and kinetics of discontinuous precipitation (DP) and discontinuous coarsening (DC) in solution treated and isothermally aged Al-Zn alloys containing 39.3 and 59.3 at.% Zn have been investigated at temperatures ranging from 323 to 523 K by light microscopy, electron microscopy and X-ray diffraction. At all aging temperatures the supersaturated α solid solution was observed to decompose rapidly by DP into a lamellar mixture of solute depleted α phase and β phase precipitate. DP occurred so rapidly in the 59.5 at.% Zn alloy that the heat of transformation raised the temperature of the alloy significantly. With further aging a slower DC reaction transformed the lamellar DP into a coarser lamellar structure of the same two phases; however, the composition of the α phase of the DC was closer to the equilibrium solvus composition than that of the DP. With still further aging a second, much slower DC reaction was observed to decompose the lamellar product of the first DC reaction in the 59.5 at.% Zn alloy into a still coarser lamellar structure. Analysis of the kinetics of both the DP and DC reactions showed them to be controlled by boundary diffusion in the advancing reaction interface. Reaction front migration rates for both DP and DC increased markedly with increasing Zn content. This increase seems to be associated partially with an increase in boundary diffusivity with increasing Zn content.     

Transformation behavior of nearly stoichiometric Ni-Mn alloys

The transformation behavior of Ni-Mn alloys in the vicinity of the stoichiometric composition has been studied using transmission electron microscopy, X-ray diffraction, optical microscopy, and electrical resistivity measurements. The transformation behavior was found to be markedly different in Mn-rich alloys and Ni-rich alloys. In Mn-rich alloys a martensitic transformation between L2₀ (B2) and L1₀ structures takes place, which possesses many features common to alloys exhibiting a thermoelastic martensitic transformation. On the other hand, in Ni-rich alloys an order-disorder transformation between A2 and L1₀ structures occurs. The martensitic transformation features {111} transformation twins as the transformation substructure while the ordering reaction involves {101} order twins. In the Mn-rich alloys, the martensitic phase, if either slowly cooled or annealed at intermediate temperatures, becomes “tempered”, resulting in a noncrystallographic, essentially featureless microstructure apart from the presence of occasional {111} twins. Formerly with University of Illinois.     

On the Stability of Reversely Formed Austenite and Related Mechanism of Transformation in an Fe-Ni-Mn Martensitic Steel Aided by Electron Backscattering Diffraction and Atom Probe Tomography

The stability of reversely formed austenite and related mechanism of transformation were investigated against temperature and time in an Fe-9.6Ni-7.1Mn (at. pct) martensitic steel during intercritical annealing at a dual-phase (α + γ) region. Dilatometry, electron backscattering diffraction (EBSD), atom probe tomography (APT), and X-ray diffraction (XRD) were used to characterize the mechanism of reverse transformation. It was found that under intercritical annealing at 853 K (580 °C), when the heating rate is 20 K/s (20 °C/s), reverse transformation takes place through a mixed diffusion control mechanism, i.e., controlled by bulk diffusion and diffusion along the interface, where Ni controls the diffusion as its diffusivity is lower than that of Mn in the martensite and austenite. Increasing the intercritical annealing to 873 K (600 °C) at an identical heating rate of 20 K/s (20 °C/s) showed that reverse transformation occurs through a sequential combination of both martensitic and diffusional mechanisms. The transition temperature from diffusional to martensitic transformation was obtained close to 858 K (585 °C). Experimental results revealed that the austenite formed by the diffusional mechanism at 853 K (580 °C) mainly remains untransformed after cooling to ambient temperature due to the enrichment with Ni and Mn. It was also found that the stability of the reversely formed austenite by martensitic mechanism at 873 K (600 °C) is related to grain refinement.     

Effect of Nitrogen on the Deformation Behaviour of High‐Nitrogen Austenitic Stainless Steels

The deformation behaviour of high‐nitrogen austenitic steels with the base composition of Fe‐18Cr‐10Mn containing various contents of nitrogen was investigated. Two deformation modes including deformation‐induced martensitic transformation (DIMT) and deformation twinning (DT) were observed depending on the nitrogen content. In the alloys with lower nitrogen contents, γ→?→α' martensitic transformation sequentially occurred, whereas DT acted as a main deformation mode and DIMT was suppressed in the alloys with increasing nitrogen content. Both DIMT and DT showed strong crystallographic orientation dependence. The competing mechanism between them was discussed in terms of the variation of stacking fault energy with nitrogen content.     

Ni55Mn25Ga18Ti2高温形状记忆合金的热循环稳定性

选择双相韧化的Ni?Mn?Ga?Ti高温形状记忆合金为研究对象。制备了淬火态Ni₅₅Mn₂₅Ga₁₈Ti₂高温形状记忆合金,并对其在室温至480 ℃之间进行高达500次的相变热循环,获得了5, 10, 50, 100和500次热循环态样品。采用X射线衍射、扫描电镜、能谱仪、同步热分析仪及室温压缩等实验方法,研究了淬火态和热循环态合金样品的微观组织、相变行为、力学及记忆性能,进而分析其热循环稳定性。研究结果表明:经500次循环后,Ni₅₅Mn₂₅Ga₁₈Ti₂合金相结构和显微组织未发生明显变化,均为由非调制四方结构的板条马氏体相和面心立方富Ni的γ相组成的双相结构;随着循环次数增加,马氏体相变温度几乎不变,逆马氏体相变温度和相变滞后在循环5次后趋于稳定;抗压强度及压缩变形率波动幅度较小;形状记忆性能下降,但形状记忆应变仍保持在1.4%以上;Ni₅₅Mn₂₅Ga₁₈Ti₂高温形状记忆合金显示出良好的热循环稳定性。      

Influence of Composition and Thermomechanical Training Process on the Transformation Behavior and Shape Memory Properties of NiTi Based Alloys

The effects of composition, specially the Cu element and thermomechanical training process on the transformation and one way shape memory behavior (OWSM) of NiTi based alloys were investigated using differential scanning calorimetry and microstructural analysis. The hot rolled strips with different compositions were trained under various applied pre-strains by bending test at martensitic state. It was found that the presence of Cu in the NiTi alloy results in an improvement of the OWSM effect by reducing the transformation hysteresis and forming the longer martensitic variants with lower interfacial energy than the NiTi binary alloys. Increasing the applied pre-strain and the number of thermomechanical training cycles caused OWSM effect to decrease. Although the transformation temperature increased at the higher applied pre-strain, it was reduced during the thermomechanical training process.     

碳含量对Fe-15Mn-4.5Si-10Cr-5Ni-C系形状记忆合金性能的影响机制

 为通过调控碳含量获得形状记忆性能优异的铁基形状记忆合金,研究了3种不同碳含量对固溶时效态Fe-15Mn-4.5Si-10Cr-5Ni-C系形状记忆合金微观组织、力学性能及形状记忆效应的影响。结果表明,固溶时效态Fe-15Mn-4.5Si-10Cr-5Ni-(0.05~0.2)C合金的形状记忆效应随碳含量的增加呈现先增后减的趋势。这是由于一方面,随着碳含量的增加,碳原子的间隙固溶强化和第二相碳化物的沉淀析出强化提高奥氏体母相强度,抑制不可逆塑性变形的发生,有利于材料在受力时发生应力诱发奥氏体γ转变为ε马氏体(γ→ε),从而提高形状记忆效应。另一方面,全固溶温度随碳含量的增加而升高。由于全固溶温度的升高,固溶处理后得到的相对粗大的奥氏体晶粒造成奥氏体母相强度的降低。同时,随着碳含量的增加导致ε马氏体相变温度(M_εs)的降低,应力诱发相变过程受到抑制,不利于形状记忆效应。在不同影响机制的相互作用下,碳质量分数为0.091 8%固溶时效态试验合金的形状记忆性能最优。     

Nb元素对Zr-Ti基生物材料力学性能和耐腐蚀性能的影响

通过真空非自耗电弧熔炼炉制备Zr-Ti-xNb(x=6、8、10,摩尔分数,%,下同)合金,采用锻造和β单相区固溶热处理工艺进一步加工铸锭,通过对材料微观组织、力学性能和耐腐蚀性能的表征,研究Nb元素对Zr-Ti基生物材料力学性能和耐腐蚀性能的影响。结果显示,Zr-Ti-xNb(x=6、8、10)合金均由β相和α″相组成,随着Nb元素含量增加,β相含量增加,α″相含量降低,Nb元素添加提高了合金中β相的稳定性。同时Nb含量增加,合金屈服强度由360 MPa增加至780 MPa,固溶强化效应明显,在变形过程中出现了应力诱发马氏体相变现象,极大提高材料的抗拉强度和塑性。同时可以较好地提高合金的耐腐蚀性能,实验表明三种材料在生理盐水中均表现出较强的耐腐蚀性能。     

Effect of thermally activated mechanisms on the martensitic transformation of modified Cu-Al-Ni alloys

The influence of thermal activation on the martensitic transformation of Cu-Al-Ni alloys containing boron and manganese has been studied by measuring the effect of heating/cooling rate during thermal cycling on the fraction transformed at a given time. The activation energies measured for the reverse and direct transformation of 70 and 140 kJ mol⁻¹ respectively have been interpreted in terms of the mechanisms regarding nucleation and growth of the martensitic phase. The different mechanisms proposed together with the driving forces involved, the type of interface and the change in the ordered state of the structure have been used to discuss the stability of the transformation in the alloys with different manganese content.