Fe-Ni-Si基奥氏体时效合金的马氏体相变和形状记忆效应

It is well known that the morphologies of the α martensite formed from the γ phase in ferrous alloys are classified into five types of lath, butterfly, (225)A type plate,lenticular and thin-plate. Among those α martensites, onlythe thinplate martensite, which is characterized by containing a high density of transformation twins, has a potential of exhibiting a perfect shape memory (SM) effect.Recently the present authors found in Fe-Ni-Si alloys that the thin-plate martensite is formed by the introduction of fine and coherent γ-(Ni,Fe)3Si particles with a L12 ordered structure in the austenite matrix due to ausaging. In the present study, the SM properties of the ausaged Fe-Ni-Si alloys with the thin-plate martensite are investigated by a conventional bending-test. The effects of the addition of Co to the Fe-Ni-Si alloys on the martensitic transformation and the SM properties are also investigated. It is shown that while the ausaged Fe-Ni-Si ternary alloys exhibit an imperfect SM effect due to reverse transformation from stress-induced thin-plate martensite to austenite, the SM properties are improved by the addition of Co. An almost perfect SM effect is confirmed in the Fe-Ni-Si-Co alloys by heating to 1 100 ℃ after deformation at -196 ℃.     

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.     

Effects of Temperature and Alloying Elements on γ Phase Fraction of Grain-oriented Silicon Steel

The effects of temperature and alloying elements on γ phase fraction of grain-oriented silicon steel,which contained 2.97-3.42mass% Si and 0.028-0.058mass% C,were studied by microstructure observation and statistics.Furthermore,the quantitative relationships of temperature as well as C,Si,and Mn contents to γ phase fraction were obtained by numerical fitting.The experimental results show that γ phase fraction firstly increases with increasing temperature,reaches a maximum and then decreases in the temperature range of 900-1 250 ℃.The temperature corresponding to the maximum γ phase fraction is about 1 150-1 200℃.Meanwhile,the γ phase fractions in steels at the same temperature have some differences because of different contents of various alloying elements.The verification results show that the values of γ phase fractions to C,Si,and Mn contents at the specific temperatures,which were obtained by multiple linear regression method,agree well with the measured values.In addition,the values of γ phase fractions to C,Si,and Mn contents in the temperature range of 900-1 250℃,which were obtained by binomial regression method,agree with the measured values when the contents of Mn and soluble Al are not more than 0.320mass% and 0.034mass%,respectively.The obtained equations can carry out the approximate prediction of γ phase fractions of grain-oriented silicon steels during the hot rolling process.     

Microstructural Tailoring During Solid-State Transformation by EPM

Ni-Mn-Ga ferromagnetic shape memory alloys can generate large output with fast dynamic response at the application of the magnetic field and is considered as a new class of functional materials.Since the martensite of these alloys is highly magnetocrystalline anisotropic,introducing a magnetic field during their martensitic transformation could be an effective way to control variant distribution and realize texturation.In this work,some of our recent results achieved in microstructural and crystallographic texture modification by EPM(Electromagnetic Processing of Materials)during solid-state phase transformations of Ni-Mn-Ga alloys were summarized.Moreover,the entropy change induced by magnetic field in Ni-Mn-Ga melt-spun ribbons were also presented.     

Effects of Chromium,Vanadium and Austenite Deformation on Transformation Behaviors of High-strength Spring Steels

The phase transformation behavior during continuous cooling of high-strength spring steels containing dif-ferent amounts of Cr was studied.Furthermore,the effects of combining Cr with V as well as austenite deformation on the transformation kinetics were investigated in the method of dilatometry and metallography hardness.The re-sults showed that,with the increase of Cr,the pearlite transformation field was enlarged,the ferrite transformation field was narrowed,and the entire phase field shifted to the right.With the addition of V,the start transformation temperature of undercooling austenite (Ar3 )was gradually increased,but the ferrite and pearlite transformation fields were not affected.Besides,the minimum critical cooling rate of martensitic transformation was also reduced.In addition,the dynamic continuous cooling transformation (CCT)curve moves to the top left compared with the static CCT curve.The transformed microstructures showed that the addition of V and the deformation not only refined the overall transformed microstructures but also reduced the lamellar spacing of pearlite.The alloying elements Cr and V promoted the Vickers hardness.However,the effect of Cr on the Vickers hardness of martensite was stronger and the influence of V on that of pearlite was stronger.Moreover,the Vickers hardness affected by the austenite deform-ation was more complex and strongly depended on the transformed microstructures.     

Effect of Cerium on Microstructures of Hard Alloys

Microstructures and crack extending characteristic of the YG8R,YT5R and YT14R hard alloysadding a trace cerium were studied by AEM and HVEM with a tensile holder.In the hard alloys addingcerium,the compounds of Ce_2O_3 or Ce_2O_2S could be formed,extending of stacking faults and transforma-tion from fcc Co to hcp Co were suppressed,volume fraction of fcc Co in the alloys was increased,andstrength of Co and(TiW)C phases and grain boundaries were raised.Plastic deformation in Co phase nearedges of the tensile cracks was more strong,and the tensile cracks could pass through some smaller WCgrains.     

Study on Gd-Si-Ge Alloys Using Domestic Gd

To evaluate the possibility of using Gd-Si-Ge alloys in magnetic refrigerators, samples of Gd-Si-Ge alloys were made of domestic Gd. The magnetocaloric effect of samples was estimated by magnetic entropy change (-△ASm) calculated from M-H curves according to Maxwell relation. The first order phase transformation was destroyed due to the impuritiesin the commercial Gd, so that no giant magnetocaloric effect was found. The samples made of purified Gd exhibit first order phase transformation, and the -△Sm is basically consistent with the published data of Ames laboratory, USA. This work proves that Gd-Si-Ge alloys made of domestic Gd can be utilized in magnetic refrigerators.     

Solidification behavior, microstructure and tensile properties of ZK60-Er magnesium alloys

ZK60-Er (erbium) alloys were made by melting ZK60 and Mg-Er magnesium alloys (20 wt.% Er) in an electric resistance furnace. The contents of Er were 0, 0.5, 1, 2, 3 wt.%, respectively. The influence of Er on solidification behavior, microstructure, corrosion resistant and mechanical properties of ZK60 magnesium alloy was studied. The results showed that long rod-like γ phase (ErZn5) formed during solidification increased with increasing Er content in the range investigated, which resulted in the decrease of the amount of galvanic couplings between phase particles and alloy matrix and the marked improvement of corrosion resistant. It was also found that elongation of the alloys decreased with increasing Er content, but tensile strength of the alloys were improved by the addition of Er due to the strengthening effect of γ phases distributing along grain boundaries.     

Influence of Zn Addition on Microstructures and Martensitic Transformation in CuZr-based Alloys

Compositional dependences on microstructures and martensitic transformation behaviors in(Cu_(0.5)Zr_(0.5))_(100-x)Zn_x(x=1.5,2.5,4.5,7.0,10.0,and 14.0at.%)alloys were investigated.It was found that CuZr martensites were present in the present alloys.With increasing Zn content,the volume fractions of CuZr martensitic crystals and B2 CuZr phase gradually decrease and increase,respectively.With the addition of high Zn contents(i.e.,7.0,10.0,and 14.0at.%),the matrix proves to be eutectic.Thermal analysis results show that the initial martensitic transformation temperature(M_s)decreases from(412±5)K to(329±5)K as the Zn content increases from 1.5at.% to14.0at.%.The values of Msof Cu-Zr-Zn shape memory alloys are inversely proportional to the number and concentrations of valence electrons(i.e.,e_v/a and c_v),respectively,implying that the martensitic transformation in CuZrZn alloys could be of electronic nature.     

Co-Cr系相平衡的热力学计算和fcc相的磁性诱导相分离

Two-phase equilibria between the ferromagnetic fcc and the paramagnetic fcc phase from 800 ℃ to 900 ℃ in the Co-rich region have been detected by the diffusion couple technique. Two phase separation region of the fcc has been confirmed along the Curie temperature. The phase equilibria including the present results and the thermodynamic data of the Co-Cr system reported in the literature were analyzed on the basis of the thermodynamic evaluation. A set of thermodynarnic values for the liquid, fcc, hcp, bcc, sigma phases was obtained. The calculated phase equilibria were in good agreement with most of the experimental data.     

Fe对Ni-Mn-Ga形状记忆合金相变和力学性能的影响

研究了Fe含量对Ni₅₆Mn_25-xFe_xGa₁₉(x=0~10)合金的微观组织结构、相变行为、力学性能和记忆特性的影响规律.当x ≤ 4时,Ni₅₆Mn_25-xFe_xGa₁₉合金仍然保持着单一的四方结构马氏体相;当x ≥ 6时,合金呈现为马氏体相和面心立方γ相组成的双相结构.相对于马氏体相,γ相为富Ni和富Fe相,其含量随Fe含量的增加而增加.随着Fe含量增加,合金的马氏体相变温度逐渐降低,其峰值温度从x=0时的356℃降低至x=10时的170℃,这主要归因于马氏体相尺寸因素和电子浓度的综合作用.通过添加Fe替代Mn在合金中引入的γ相可提高合金的强度和塑性,但最大形状记忆回复应变从x=0时的5.0%降低到x=6时的2.0%.      

A transmission electron microscopy study of the mechanisms of strengthening in heat-treated Co-Cr-Mo-C alloys

Microstructures produced in the Co-Cr-Mo-C alloy H.S.21 were observed by transmission electron microscopy in cast specimens following solutionizing at 1230°C and aging at 650°C and in low-carbon wrought specimens following solutionizing and aging at 650°C and 750°C. In all cases, aging was found to promote the formation of fcc stacking faults and to cause an initial martensitic transformation from the fcc phase to a heavily faulted hep structure. Precipitate formation was observed in hcp areas of the cast material after 20 h at 650°C and in hcp areas of wrought material after 20 h at 750°C. Prolonged aging at 750°C produced a transformation in the hcp structure of wrought specimens, with a relatively fault-free structure replacing the heavily faulted martensitic form. Interruption of fcc slip by both fcc stacking faults and bands of hcp phase was found to be the principal strengthening mechanism activated by aging. Precipitate formation in the hcp plays an increasingly significant role as aging time is increased. This microstructural information is used to explain the observed tensile properties of these alloys after the heat treatments mentioned.     

High-resolution transmission electron microscopy investigation of the face-centered cubic/hexagonal close-packed martensite transformation in Co-31.8 wt pct Ni alloy: Part 2. Plate intersections,extended defects,and nucleation mechanisms

The face-centered cubic/hexagonal close-packed (fcc/hcp) martensite phase transformation in a Co-31.8 wt pct Ni alloy was studied by high-resolution transmission electron microscopy (HRTEM). The HRTEM was used to study the structure and properties of intersections between martensite plates and other defects observed in the alloy such as stacking fault tetrahedra (SFT) and Z-type defects. The HRTEM was also used to attempt to determine if various proposed mechanisms for the fcc/hcp martensite transformation were operating. There is evidence to suggest that the reflection mechanism proposed by Bollmann and the dipole mechanism proposed by Hirth are active in the fcc/hcp martensitic transformation, although the evidence is not completely certain in either case. Growth of the hcp phase by a four- or six-plane mechanism as proposed by Mahajanet al. is possible in theory but was not observed in this study. Transformation by previously proposed pole mechanisms was also not observed in this study, although evidence for a new type of pole mechanism was found. The formation of SFT along the fcc/hcp martensite interface was observed to occur by the cross-slip of Shockley partial dislocations out of the fcc/hcp interface onto conjugate fcc matrix planes, followed by further cross-slip to form the SFT, as previously observed for grain boundaries in fcc alloys.     

A transmission electron microscopy study of the mechanisms of strengthening in heat-treated Co-Cr-Mo-C alloys

Microstructures produced in the Co-Cr-Mo-C alloy H.S.21 were observed by transmission electron microscopy in cast specimens following solutionizing at 1230°C and aging at 650°C and in low-carbon wrought specimens following solutionizing and aging at 650°C and 750°C. In all cases, aging was found to promote the formation of fcc stacking faults and to cause an initial martensitic transformation from the fcc phase to a heavily faulted hep structure. Precipitate formation was observed in hcp areas of the cast material after 20 h at 650°C and in hcp areas of wrought material after 20 h at 750°C. Prolonged aging at 750°C produced a transformation in the hcp structure of wrought specimens, with a relatively fault-free structure replacing the heavily faulted martensitic form. Interruption of fcc slip by both fcc stacking faults and bands of hcp phase was found to be the principal strengthening mechanism activated by aging. Precipitate formation in the hcp plays an increasingly significant role as aging time is increased. This microstructural information is used to explain the observed tensile properties of these alloys after the heat treatments mentioned.     

Effect of W Contents on Martensitic Transformation and Shape Memory Effect in Co-Al-W Alloys

To clarify the effect of W contents on the shape memory effect (SME) in the Co-Al alloys and its influencing mechanism, the SME, martensitic transformation, and deformation behavior were studied in the Co-7Al-xW (x = 0, 4, 6, 9 wt pct) alloys. The results showed that the additions of W all deteriorated the SME in Co-7Al alloy when deformed at room temperature. However, when deformed in liquid nitrogen, the SME in Co-7Al alloy could be remarkably improved from 43 to 78 pct after the addition of 4 pct W, above which the SME decreased rapidly with the increase of W content although the yield strength of the parent phase rose due to the solution strengthening of W. The deterioration in SME induced by the excessive addition of W could be ascribed to its resulting significant drop of the start temperature of martensitic transformation.     

Work strengthening by a deformation-induced phase transformation in “MP alloys”

Work strengthening and microstructure were investigated for a class of alloys, designated “MP Alloys”, containing 20 pct Cr, 10 pct Mo, and the remainder cobalt and nickel in proportions ranging from 60Co∶10Ni to 30Co∶40Ni. These alloys, in the fully annealed, homogenized condition, have a fcc structure with yield strengths ranging from about 45 to 60 ksi. Deformation at room temperature rapidly increases the yield strength of the alloys to about 250 ksi. Structural analyses by X-ray and electron diffraction techniques indicate that this marked increase in strength is associated with a deformation-induced martensitic transformation forming a network of extremely thin hcp platelets within the fcc grains. The nature of this martensitic transformation was studied as a function of alloy composition, deformation temperature, and structural variables, such as the platelet size, thec/a ratio of the hcp phase, and twinning.     

Molecular-dynamic simulations of martensitic transformation of cobalt

With a potential-energy function of Co described by the embedded-atom method (EAM), molecular-dynamics (MD) simulations were performed for a series of initial fcc configurations with different types of dislocations or preset hcp embryos. The gliding process of a Shockley dislocation on a closepacked plane has been observed, which starts from the origin of the dislocation and proceeds at a high speed of 280 m/s toward a certain direction. An atom which has been swept by the dislocation line was detected to contribute a displacement close to the Burgers vector of a Shockley dislocation. It is in this way that a new stacking sequence is produced and an hcp lamella grows in the fcc structure. A similar gliding process has been observed in the case where an intrinsic stacking fault is preexisting in the fcc structure. The transformation is, again, toward forming a local hcp region. These results prove that a special dislocation in the fcc structure can act as an embryo of the hcp, as described in many dislocation mechanisms of the martensitic transformation. The fcc → hcp phase-tranformation process of Co has been further reproduced by a simulation initiated from an fcc/hcp two-phase configuration. It yields a single hcp crystal as the final transformed product.     

燃烧合成法制备CoCrMo合金

采用燃烧合成法成功制备了CoCr Mo合金。燃烧合成的合金是由钴的两种固溶体组成,分别为密排六方的ε-CoCr Mo相和面心立方的γ-CoCr Mo相;渣相主要为Al2O3;合金的微观结构为铸态树枝晶,并且存在枝晶偏析现象,枝晶上富钴,枝晶间富钼,铬分布比较均匀;此外,燃烧合成过程中可能产生马氏体相变使γ-Co相转变为ε-Co相,并且在马氏体片中出现了带状亚结构。