CN101215678A - Training-free casting iron-base shape memory alloy containing high temperature ferrite - Google Patents
Training-free casting iron-base shape memory alloy containing high temperature ferrite Download PDFInfo
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- CN101215678A CN101215678A CNA2008100452022A CN200810045202A CN101215678A CN 101215678 A CN101215678 A CN 101215678A CN A2008100452022 A CNA2008100452022 A CN A2008100452022A CN 200810045202 A CN200810045202 A CN 200810045202A CN 101215678 A CN101215678 A CN 101215678A
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Abstract
The invention discloses a no- training casting Fe-based shape memory alloy with high-temperature ferrite and a method for preparation. The alloy comprises elements which are ferric, manganese, silicon, chromium, nickel, titanium, niobium, carbon and nitrogen, the weight percentages of various elements are that the manganese is 12-32 percent, the silicon is 4-8 percent, the chromium is 0-12 percent, the nickel is 0-6 percent, the titanium is 0-2 percent, the niobium is 0-2 percent, the carbon is 0.02-0.25 percent, the nitrogen is 0.02-0.2 percent, and the other is ferric. The concrete method for preparation is that after being cast, the alloy which comprises the above components is obtained through melting is kept in 400-1200 DEG C for 15-60 minutes to be water-cooled or air-cooled, the invention is characterized in that the high-temperature ferrite exists in an austenitic matrix of the cast alloy. The shape memory alloy which is prepared by the method has the advantages of simple production process, high shape memory effect and low cost.
Description
Technical field
The present invention relates to the shape memory alloy field, be specifically related to a kind of iron-base marmem and preparation method thereof.It is simple to have production technique with the shape memory alloy of this method preparation, the high and low advantage of cost of shape memory effect.
Background technology
Shape memory effect is meant when certain material after the distortion is heated above certain temperature can all or part ofly return to original undeformed shape.Alloy with this effect is called shape memory alloy, and it is a kind of new function material that integrates perception and drive.Up to now, find that the alloy with shape memory effect has tens of kinds, but have the shape memory alloy of better application value at present, can be divided into three major types: 1. Ti-Ni alloy: Ti-Ni by composition; 2. copper base alloy: Cu-Zn-Al, Cu-Al-Ni; 3. ferrous alloy: Fe-Mn-Si, Fe-Ni-Co-Ti.
Compare with the NiTi shape memory alloy of costliness, FeMnSi base alloy because of with low cost, intensity is high, can weld and easily processing, has just attracted lot of domestic and foreign scholar's research since nineteen eighty-two is found.Yet, up to the present, can not satisfy the requirement that engineering is used without the replied deflection of the polycrystalline FeMnSi of special processing base alloy 1.5～2% (deflections * recovery of shape rate) only.Mainly improve the replied deflection of polycrystalline FeMnSi base alloy at present by the mode of following two kinds of special processings:
(1) the hot mechanical cycles processing that room temperature 4～6% distortion for several times add near process annealing 600 ℃ is promptly carried out in hot mechanical cycles training, and this is to improve the most significant method of alloy shape memory effect at present.But this processing has not only increased preparation cost, and complex-shaped element is difficult to carry out.Therefore, be difficult to obtain industrialized application.
(2) distortion back timeliness thermal treatment: the ZL03107408.1 patent disclosure a kind of interpolation Nb, the FeMnSi of C is the processing heat treating method of shape memory alloy, promptly earlier be alloy with FeMnSi 500～800 ℃ carry out the 10-30% hot rolling deformation after, 400～1000 ℃ of timeliness NbC is separated out again, and then improve the processing heat treating method of alloy shape memory effect, reached level after the hot mechanical cycles training 5 times through the shape memory effect of this processing alloy.Patent ZL02133699.7 disclose a kind of elder generation with FeMnSi base alloy after room temperature is carried out 5～25% distortion, make in austenite crystal intragranular directivity 750～950 ℃ of timeliness again and separate out Cr
23C
6Second phase, and then improve the shape memory effect of alloy also can reach level after the hot mechanical cycles training 5 times through the shape memory effect of this processing alloy.But the essence of ageing treatment all is hot mechanical cycles training after these two kinds of distortion, just frequency of training is reduced to 1 time, and the ZL03107408.1 patent also need adopt high temperature deformation, complex-shaped element still is difficult to carry out, thereby all is difficult to obtain industrialized application.
Summary of the invention
Purpose of the present invention is exactly the problem that exists at prior art, provides a kind of and utilizes conventional castmethod preparation to exempt from the method for the good FeMnSi base marmem of training shapes memory effect.
The research (ZL02133699.7) in result of study that analysis-by-synthesis is present and our early stage, we think that the condition that the basic alloy of FeMnSi has the excellent in shape memory effect is that stress-induced austenite γ → ε martensitic transformation forms in the mode of compartmentation, promptly the ε martensite that forms at an austenite crystal intragranular has been divided into several zones, and the martensite that only exists a kind of orientation or orientation to be dominant in each zone.Can reduce and avoid the collision of different orientation and different zones martensite bundle when being out of shape like this, guarantee to obtain the high stress-induced of interface movement reversibility, and then obtain good shape memory effect.The essence that hot mechanical cycles significantly improves the alloy memory effect has realized above-mentioned condition just---stress-induced forms in the mode of compartmentation.Just in order to realize this condition, it produces a large amount of equally distributed stacking faults in advance in the different zones of austenite crystal intragranular, and stress-induced can serve as nuclear embryo forming core and grow up with these faults that is pre-existing in when making distortion.
Recently, in earlier stage utilize deformation induced aging to separate out the second region austenite at us, and significantly improve on the basis of alloy shape memory effect (ZL02133699.7), imperfection based on high temperature ferrite δ in the austenitic stainless steel process of setting → γ austenite solid state transformation, utilize the residual high temperature ferrite δ effect that compartmentation is cut apart to austenite crystal, see Fig. 1 (a), directly realized FeMnSi base alloy have the excellent in shape memory effect condition---stress-induced austenite γ → ε martensitic transformation forms in the mode of compartmentation, the shape memory effect of alloy is significantly improved.
The present invention is a kind of ferritic training-free casting iron-base shape memory alloy of high temperature that contains, it be contain Fe, Mn at least, Si is a shape memory alloy as the FeMnSi of main chemical compositions, the weight percent content of each element is: Mn 12～32%, and Si 4～8%, Cr 0～12%, Ni 0～6%, and Ti 0～2%, and Nb 0～2%, C 0.02～0.25%, N 0.02～0.2%, and surplus is Fe, and there is high temperature ferrite δ in tissue signature in austenitic matrix.
The present invention is based on the imperfection of high temperature ferrite δ in the austenitic stainless steel process of setting → γ austenite solid state transformation, and being used for of utilizing the residual high temperature ferrite δ that do not change compartmentation is cut apart to austenite crystal realizes that directly FeMnSi base alloy has the condition of excellent in shape memory effect.Because the chemical ingredients in the alloy is Cr by formula
Eq=Cr+1.5Si+2Nb+3Ti and Ni
Eq=Ni+0.31Mn+22C+14.2N (element is represented the weight percentage of institute's addition element) is converted into chromium equivalent Cr
EqWith nickel equivalent Ni
EqAfter ratio C r
Eq/ Ni
Eq＜1.25 o'clock, the pattern of solidifying of alloy was liquid phase L → L+ γ → γ, is monophasic austenite γ under the room temperature, does not have high temperature ferrite δ; Work as Cr
Eq/ Ni
EqSatisfy 1.25＜Cr
Eq/ Ni
Eq＜1.48 o'clock, the pattern of solidifying of alloy was liquid phase L → L+ γ → L+ γ+δ → γ+δ; Work as Cr
Eq/ Ni
EqSatisfy 1.48＜Cr
Eq/ Ni
Eq＜1.95, the pattern of solidifying of alloy is liquid phase L → L+ δ → L+ γ+δ → γ+δ; Work as Cr
Eq/ Ni
EqSatisfy Cr
Eq/ Ni
Eq＞1.95, the pattern of solidifying of alloy is L → L+ δ → δ → γ+δ.Therefore in order to guarantee that alloy has high temperature delta ferrite, a Cr through casting back room temperature is residual
Eq/ Ni
EqMust be greater than 1.25, what this was a patent of the present invention with technology at present is maximum different.The Fe base marmem is carried out to and sets up timing separately at present, all is based on to obtain monophasic austenitic matrix, so all will handle through the pyritous austenitizing.Aforementioned ZL03107408.1 and ZL02132907.9 patent just are based on this principle.
In order to obtain preferable shape memory effect, the volumn concentration of high temperature delta ferrite should be controlled in 0.2～5%.Delta ferrite level is lower than at 1% o'clock, the compartmentation of austenite crystal is cut apart not obvious, not remarkable to the raising of shape memory effect; But delta ferrite level is greater than after 2.5%, and the increase of ferrite content can reduce the quantity of stress-induced, and is also unfavorable to the shape memory effect of alloy.When the content of high temperature delta ferrite 1～2.5% the time, when ferritic pattern is lath-shaped, the compartmentation of austenite crystal is cut apart the most effective, the most remarkable to the raising of alloy shape memory effect, at this moment, Cr
Eq/ Ni
EqRatio satisfy 1.55＜Cr
Eq/ Ni
Eq＜2.0.
In addition, for the component segregation for elimination casting stress and microcosmic, alloy generally will carry out the 400 ℃～stress relief annealing of 1200 ℃ of temperature ranges and the thermal treatment of homogenizing.But temperature is too high, can cause the decomposition of high temperature ferrite δ, weakens effect is cut apart in austenitic compartmentation.Therefore, in order to guarantee the residual high temperature ferrite δ effect that compartmentation is cut apart to austenite crystal, preferable thermal treatment temp is between 500 ℃～1000 ℃.
Compared with prior art, the present invention has following advantage:
1) be at present truly exempt from train height can reply the FeMnSi base alloy of deflection, and utilize conventional castmethod to realize.Therefore it is simple to have technology, the advantage that preparation cost is cheap.
2) in δ+γ two-phase structure, obtain good shape memory effect, broken the traditional concept that only in austenite γ single phase structure, could obtain good shape memory effect.So the novel FeMnSi base alloy that the present invention exempts to train height can reply deflection for exploitation provides a kind of brand-new research thinking and technology of preparing.
Description of drawings
Fig. 1 is the metallographic microstructure figure of the casting alloy of different heat treatment state.(a) among the figure is the metallographic of as cast condition, (b) is 700 ℃ * 30min water-cooled, is 1000 ℃ * 30min water-cooled (c), and black wherein is organized as the high temperature ferrite.
Fig. 2 is the X-Ray diffraction spectra of cast alloy.Illustrate and have high temperature ferrite δ phase in the austenitic matrix.
Fig. 3 is the magnetzation curve of the casting alloy of different heat treatment state.Explanation is with the raising of thermal treatment temp, and the plain cognition of part high temperature iron is decomposed.
Embodiment
Provide embodiment below, so that the invention will be further described.
Melting is obtained by chemical ingredients Fe, Mn, Si, Cr, Ni, Ti, Nb, and after the elementary composition alloy casting of C and N, cast alloy is again through 400 ℃～1200 ℃ insulation 15min～60min, water-cooled or air cooling.The method of employing tensile deformation is tested the shape memory effect after as cast condition and the treatment of different temperature respectively; Adopt the ferrite surveying instrument to carry out the mensuration of high temperature ferrite content.Measuring result is seen attached list.For effect more of the present invention, the Fe28Mn6Si5Cr alloy that gives the ZL03107408.1 patent disclosure in the subordinate list is the back shape memory effect of timeliness (comparative example 2) of (comparative example 1) and distortion after overheated mechanical cycles training 5 times respectively.Data in the table clearly illustrate that: the shape memory effect of alloy of the present invention has not only reached at present after overheated mechanical cycles training 5 times and the level of distortion back timeliness, and the shape memory effect of the alloy that has is also a little more than this level.
In order to verify the ferritic existence of high temperature, and understand the influence of ferritic pattern and content to the alloy shape memory effect, the present invention has carried out the observation of metallographic structure to the sample of embodiment 5 different states, adopt X-Ray diffraction analysis method that thing is characterized mutually, VSM has analyzed magnetic performance by vibrating sample magnetometer.(a) among Fig. 1 is the metallographic of as cast condition, (b) is 700 ℃ * 30min water-cooled, is 1000 ℃ * 30min water-cooled (c), and black wherein is organized as the high temperature ferrite; Fig. 2 has provided the X-Ray diffraction spectra of as cast condition, has confirmed the ferritic existence of high temperature; Fig. 3 has provided as cast condition, 700 ℃ * 30min water-cooled and magnetzation curve 1000 ℃ * 30min water-cooled have also confirmed the ferritic existence of high temperature, also show the raising with thermal treatment temp simultaneously, the plain cognition of part high temperature iron is decomposed, and this mensuration with the high temperature ferrite content is consistent.
| Embodiment | Comparative example 1 | Comparative example 2 | ||||||||||
| |
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |||
| Chemical ingredients (weight percent) | Mn | 32 | 28 | 19 | 16 | 14 | 14 | 19 | 14 | 16 | 28 | 28 |
| Si | 6 | 6.5 | 5.5 | 5 | 5 | 6 | 6 | 6 | 6 | 6 | 6 | |
| Cr | / | 5 | 10 | 9 | 8 | 9 | 9 | 9 | 12 | 5 | 5 | |
| Ni | / | / | 5 | 4 | 4 | 4 | 5 | 4 | 5 | / | / | |
| Ti | 1.5 | / | 0.55 | / | 0.05 | / | / | / | / | / | / | |
| Nb | / | 1.5 | / | 0.55 | / | / | / | / | / | / | / | |
| C | 0.03 | 0.2 | 0.1 | 0.06 | 0.03 | 0.16 | 0.02 | 0.02 | 0.02 | / | / | |
| N | / | / | / | / | / | / | 0.06 | 0.16 | / | / | / | |
| Fe | Bal. | Bal. | Bal. | Bal. | Bal. | Bal. | Bal. | Bal. | Bal. | Bal. | Bal. | |
| Cr eq/Ni eq | 1.27 | 1.36 | 1.52 | 1.71 | 1.74 | 1.52 | 1.48 | 1.63 | 2.02 | Through the shape memory effect during 5% tensile deformation after 5 hot mechanical cycles training 5 times is 84% | Behind 600 ℃ of rolling deformations, again in 800 ℃ of timeliness after 10 minutes, the shape memory effect during 5% tensile deformation is 84% | |
| Shape memory effect (5 % tensile deformation) | As cast condition | 45％ | 51％ | 66％ | 74％ | 72％ | 68％ | 72％ | 75％ | 40％ | ||
| 500 ℃ * 30min water-cooled | 67％ | 72％ | 75％ | 81％ | 80％ | 82％ | 80％ | 86％ | 62％ | |||
| 700 ℃ * 15min water-cooled | 73％ | 78％ | 80％ | 86％ | 86％ | 85％ | 86％ | 89％ | 71％ | |||
| 700 ℃ * 30min water-cooled | 77％ | 80％ | 83％ | 88％ | 90％ | 86％ | 87％ | 89％ | 76％ | |||
| 700 ℃ * 60min water-cooled | 72％ | 81％ | 79％ | 85％ | 87％ | 80％ | 83％ | 84％ | 70％ | |||
| 700 ℃ * 30min air cooling | 74％ | 79％ | 82％ | 87％ | 88％ | 86％ | 85％ | 86％ | 72％ | |||
| 900 ℃ * 30min water-cooled | 64％ | 65％ | 69％ | 78％ | 80％ | 73％ | 76％ | 80％ | 65％ | |||
| 1000 ℃ * 30min water-cooled | 50％ | 52％ | 60％ | 69％ | 71％ | 62％ | 65％ | 69％ | 48％ | |||
| Ferrite content | As cast condition | 0.5％ | 0.6 | 1.1％ | 1.6％ | 1.6％ | 1.0％ | 1.2％ | 1.5％ | 2.5％ | ||
| 400 ℃ * 30min water-cooled | 0.5％ | 0.6 | 1.0％ | 1.6％ | 1.6％ | 1.0％ | 1.0％ | 1.5％ | 2.5％ | |||
| 700 ℃ * 30min water-cooled | 0.4％ | 0.5 | 0.8％ | 1.3％ | 1.3％ | 0.9％ | 0.9％ | 1.4％ | 2.0％ | |||
| 900 ℃ * 30min water-cooled | 0.3％ | 0.4 | 0.7％ | 1.1％ | 1.1％ | 0.8％ | 0.8％ | 1.2％ | 1.8％ | |||
| 1000 ℃ * 30min water-cooled | 0.2％ | 0.3 | 0.6％ | 0.8％ | 0.9％ | 0.7％ | 0.6％ | 1.0％ | 1.6％ | |||
Claims (8)
1. exempt to train iron-base marmem for one kind, this alloy is by Fe, Mn, Si, Cr, Ni, Ti, Nb, and C and N are elementary composition, it is characterized in that having the high temperature ferrite in the austenitic matrix of alloy, the weight percent content of each element is: Mn 12～32%, and Si 4～8%, and Cr 0～12%, Ni 0～6%, Ti 0～2%, and Nb 0～2%, and C 0.02～0.25%, N 0.02～0.2%, and surplus is Fe.
2. one kind prepares the described preparation method who exempts to train iron-base marmem of claim 1, be that melting is obtained by chemical ingredients Fe, Mn, Si, Cr, Ni, Ti, Nb, the elementary composition alloy of C and N is after casting, cast alloy is again through 400 ℃～1200 ℃ insulation 15min～60min, water-cooled or air cooling is characterized in that having the high temperature ferrite in the austenitic matrix of cast alloy; The weight percent content of each element is: Mn 12～32%, and Si 4～8%, and Cr 0～12%, and Ni 0～6%, and Ti 0～2%, and Nb 0～2%, and C 0.02～0.25%, and N 0.02～0.2%, and surplus is Fe.
3. the preparation method who exempts to train iron-base marmem according to claim 2, the chemical ingredients that it is characterized in that alloy is Cr by formula
Eq=Cr+1.5Si+2Nb+3Ti and Ni
Eq=Ni+0.31Mn+22C+14.2N is converted into chromium equivalent Cr
EqWith nickel equivalent Ni
EqAfter ratio C r
Eq/ Ni
Eq＞1.25.
4. the preparation method who exempts to train iron-base marmem according to claim 2 is characterized in that cast alloy is at 500 ℃～1000 ℃ insulation 15min～60min, water-cooled or air cooling.
5. exempt to train iron-base marmem according to arbitrary claim in the claim 1 to 4 is described, it is characterized in that the ferritic content of high temperature is 0.2～5%.
6. according to claim 5ly exempt to train iron-base marmem, it is characterized in that the ferritic content of high temperature is 1～2.5%.
7. the preparation method who exempts to train iron-base marmem according to claim 3 is characterized in that the chromium equivalent Cr of alloy
EqWith nickel equivalent Ni
EqRatio satisfy 1.55＜Cr
Eq/ Ni
Eq＜2.0.
8. according to claim 2ly exempt to train iron-base marmem, it is characterized in that the ferritic pattern of high temperature is a lath-shaped.
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| CN102796954A (en) * | 2012-09-08 | 2012-11-28 | 镇江忆诺唯记忆合金有限公司 | Low-manganese iron-based shape memory alloy |
| CN102796951A (en) * | 2012-09-10 | 2012-11-28 | 镇江忆诺唯记忆合金有限公司 | High ferro-manganese base shape memory alloy |
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