CN102796954A - Low-manganese iron-based shape memory alloy - Google Patents

Low-manganese iron-based shape memory alloy Download PDF

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Publication number
CN102796954A
CN102796954A CN2012103295655A CN201210329565A CN102796954A CN 102796954 A CN102796954 A CN 102796954A CN 2012103295655 A CN2012103295655 A CN 2012103295655A CN 201210329565 A CN201210329565 A CN 201210329565A CN 102796954 A CN102796954 A CN 102796954A
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alloy
shape memory
percent
response rate
annealing
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CN102796954B (en
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刘光磊
张志敏
李晓薇
司松海
陆松华
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Zhenjiang Yinuowei Shape Memory Alloys Co Ltd
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Zhenjiang Yinuowei Shape Memory Alloys Co Ltd
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Abstract

The invention discloses low-manganese iron-based shape memory alloy, which belongs to the field of memory alloy. The low-manganese iron-based shape memory alloy is characterized by comprising the following components in percentage by weight: 16 percent of Mn, 3-5 percent of Si, 5 percent of Ni, 0.1 percent of C, 0.4-1.0 percent of composite rare earth additive and the balance of Fe. The alloy is melted in a medium frequency induction electric furnace after being prepared; and when the temperature of the molten alloy is 1,530-1,550 DEG C, the molten alloy is cast into a cast ingot of phi 80*150 mm after slagging. The cast ingot which is cast is filled in a box type resistance furnace to perform annealing, wherein the annealing temperature is 1,080-1,120 DEG C and the time is 24 hours; forging and striking are performed after annealing; the forging and striking temperature is 1,000-800 DEG C; the cast ingot is forged and struck to be 10 mm*80 mm*90 mm and then is linearly cut into a specimen of 1 mm*10 mm*90 mm. The shape memory recovery rate of the cut specimen is determined by using a bending deformation method.

Description

A kind of spiegel iron base marmem
Technical field
The invention belongs to the memorial alloy field, refer in particular to a kind of spiegel iron base marmem.
Background technology
Iron-base marmem be after niti-shaped memorial alloy, copper-based shape memory alloy the exploitation the 3rd generation shape memory alloy material.With respect to Ni-Ti base and Cu base memorial alloy; The Fe base marmem is cheap with its raw materials cost, be easy to processing and manufacturing, be convenient to characteristics such as normal temperature storing, mechanical property excellence; Be used widely in industries such as oil, machinery, chemical industry, become present research focus.Iron-base marmem mainly comprises Fe-Mn-Co-Ti system, Fe-Pt system, Fe-Pd system, Fe-Mn-Si system, Fe-Ni-C system.Wherein Fe-Mn-Si is that alloy has preferably that SME and good processing properties are considered to the most promising.Fe-Mn-Si is the research of alloy near over 10 years, though obtained remarkable break-throughs, develops the alloy of multiple composition, can be used for disposable shape memory parts such as tube stub, but still be a kind of not mature enough material.Present major objective is the optimization design of alloying constituent, increases the shape memory response rate as far as possible, improves shape-memory properties.The present invention is intended to instruct it in the application aspect the production through the research alloying constituent to the influence of iron-base marmem.The present invention develops a kind of spiegel iron base marmem.
Summary of the invention
The present invention develops a kind of spiegel iron base marmem, it is characterized by: Mn 16wt%, and Si 3 ~ 5wt%, Ni 5wt%, C 0.1wt%, compound rare-earth additive 0.4 ~ 1.0 wt%, all the other are Fe.The compound rare-earth additive component is: Nd 20~28wt%, La 8~15wt%, Y 5~10wt%, Sc 4~8wt%, Ce+Pr+Eu+Gd+Tb+Ho+Er+Tm+Lu are 10~18wt%, V 2~6wt%, B 2~5wt%, Yu Weitie.In medium-frequency induction furnace, melt after the alloy preparation, when the alloy liquid temp reached 1560 ~ 1580 ℃, insulation was left standstill 3 ~ 4 minutes, when the alloy liquid temp is 1530 ~ 1550 ℃, poured into the ingot casting of Φ 80 * 150mm after skimming.The ingot casting that cast is good is put into chamber type electric resistance furnace to anneal, and purpose is to eliminate in the casting process of cooling because the internal stress that causes of cooling conditions inequality everywhere; Avoid in follow-up hot procedure, ftractureing, annealing temperature is 1080 ~ 1120 ℃, and the time is 24h; Carry out forging of foundry goods after the annealing, forging temperature is 1000 ~ 800 ℃, forges into 10mm * 80mm * 90mm; To carry out the line cutting then, cut into the sample of 1mm * 10mm * 90mm.Adopt the flexural deformation method to measure its shape memory response rate on the sample of well cutting, obtain result as shown in Figure 1.
The effect of alloying element Mn in steel is to make the expansion of γ district, forms unlimited solid solution with γ-Fe, forms limit solid solution with α-Fe.In the Fe-Mn-Si-Ni-C alloy in the present invention, when low manganese (16%), under the quenching attitude, had a considerable amount of ε martensites, and the kind of the ε martensite variants that exists is also many, in the intragranular all directions distribution is arranged all, completes a business transaction mutually and reticulate.When giving the certain initial deformation amount of this sample, have many stress-induceds to produce, so alloy have the shape memory response rate.
Elements Si plays an important role in iron-base marmem, this be because, elements Si how much be directly connected to the size that this is the stacking fault energy of alloy.As everyone knows; Iron-base marmem is low stacking fault energy alloy; The center of the fault defective that has crystals, be the prerequisite of SME, so stacking fault energy is low more as stress-induced martensite phase deformed nucleus; It is just more little to bring out the required stress of phase transformation, and the shape memory response rate is also just good more.
Fig. 1 is respectively si content in the low manganese series and is respectively 3%, 4%, 5% 3#, 4#, the shape memory response rate of 24# alloy under different dependent variables.As can beappreciated from fig. 1 with the increase of Si amount, alloy shape memory response rate obviously improves.In addition; Also will consider the influence of Si to the Fe-Mn-Si-Ni-C mechanical property, the Fe-Mn-Si-Ni-C shape memory alloy is not higher than at 5% o'clock at Si content, and plasticity is fine; No any defective after forging; Surpass this boundary, crackle can occur, and obviously worsen with the increase of Si content at the process interalloy of forging.In containing the alloy of 5.5%Si, there is ingot casting crackle to occur, and deeply forges the thin plate central authorities 15mm place that the back forms, this mainly is because the raising of Si content produces Fe in alloy 3The Si intermetallic compound, the processing characteristics rapid deterioration has limited its Application and Development.Si can improve the austenitic ys of parent phase, and the austenitic stacking fault energy of strong simultaneously reduction is considered its over-all properties in the Fe-Mn-Si-Ni-C shape memory alloy, and Si content should be controlled between 3% ~ 5%.
Among the present invention, the content of chemical element Ni is constant, remains on 5%.This considers that mainly the adding of Ni element helps the processing characteristics of alloy.The Ni element is similar to the influence and the Mn of alloy memory effect, also is the element of expansion γ austenitic area, and Ms is descended.Ni content is 5% o'clock, and memory performance is best, and it is minimum to bring out the required stress of γ → ε phase transformation this moment.
Because what the present invention adopted is that soft steel is done raw material; In common induction furnace, carry out non-vacuum melting; So what in blending process, adopt is ordinary low-carbon steel; Iron-base marmem after the melting contains the carbon about 0.10%, and this is best because contain the alloy shape memory response rate of 0.10 wt %C.It is thus clear that the carbon content of Fe-Mn-Si-Ni-C alloy has a stagnation point, when carbon content less than this threshold value the time, the shape memory response rate increases with the increase of carbon content, and the shape memory response rate will diminish when being higher than this threshold value.
Adding the compound rare-earth additive increases significantly concerning the shape memory response rate of alloy.Permanent irrecoverable slippage when the reinforcement of matrix makes initial deformation reduces, and this helps improving the shape memory response rate.The fault probability of alloy is more much bigger than the alloy that does not add the compound rare-earth additive behind the adding compound rare-earth additive, and more nucleating center and littler strain motivating force are arranged in strain-induced martensite process, so more be prone to form recoverable martensite.
Description of drawings
Fig. 1 si content is respectively 3%, 4%, 5% the shape memory response rate of alloy under different dependent variables.
Embodiment
Embodiment 1:
Alloyage Mn 16wt%, Si 3wt%, Ni 5wt%; C 0.10wt%, compound rare-earth additive 0.6wt%, all the other are Fe; In medium-frequency induction furnace, melt then, when the alloy liquid temp reached 1560 ~ 1580 ℃, insulation was left standstill 3 ~ 4 minutes; When the alloy liquid temp is 1530 ~ 1550 ℃, pour into the ingot casting of Φ 80 * 150mm after skimming.The ingot casting that cast is good is put into chamber type electric resistance furnace to anneal, and purpose is to eliminate in the casting process of cooling because the internal stress that causes of cooling conditions inequality everywhere; Avoid in follow-up hot procedure, ftractureing, annealing temperature is 1080 ~ 1120 ℃, and the time is 24h; Carry out forging of foundry goods after the annealing, forging temperature is 1000 ~ 800 ℃, forges into 10mm * 80mm * 90mm; To carry out the line cutting then, cut into the sample of 1mm * 10mm * 90mm.Adopt the flexural deformation method to measure its SME on the sample of well cutting, as shown in Figure 1, as can be seen from Figure 1, the shape memory response rate is between 42% ~ 30%.
Embodiment 2:
Alloyage Mn 16wt%, Si 4wt%, Ni 5wt%; C 0.10wt%, compound rare-earth additive 0.6wt%, all the other are Fe; In medium-frequency induction furnace, melt then, when the alloy liquid temp reached 1560 ~ 1580 ℃, insulation was left standstill 3 ~ 4 minutes; When the alloy liquid temp is 1530 ~ 1550 ℃, pour into the ingot casting of Φ 80 * 150mm after skimming.The ingot casting that cast is good is put into chamber type electric resistance furnace to anneal, and purpose is to eliminate in the casting process of cooling because the internal stress that causes of cooling conditions inequality everywhere; Avoid in follow-up hot procedure, ftractureing, annealing temperature is 1080 ~ 1120 ℃, and the time is 24h; Carry out forging of foundry goods after the annealing, forging temperature is 1000 ~ 800 ℃, forges into 10mm * 80mm * 90mm; To carry out the line cutting then, cut into the sample of 1mm * 10mm * 90mm.Adopt the flexural deformation method to measure its SME on the sample of well cutting, as shown in Figure 1, as can be seen from Figure 1, the shape memory response rate is between 51% ~ 40%.
Embodiment 3:
Alloyage Mn 16wt%, Si 5wt%, Ni 5wt%; C 0.10wt%, compound rare-earth additive 0.6wt%, all the other are Fe; In medium-frequency induction furnace, melt then, when the alloy liquid temp reached 1560 ~ 1580 ℃, insulation was left standstill 3 ~ 4 minutes; When the alloy liquid temp is 1530 ~ 1550 ℃, pour into the ingot casting of Φ 80 * 150mm after skimming.The ingot casting that cast is good is put into chamber type electric resistance furnace to anneal, and purpose is to eliminate in the casting process of cooling because the internal stress that causes of cooling conditions inequality everywhere; Avoid in follow-up hot procedure, ftractureing, annealing temperature is 1080 ~ 1120 ℃, and the time is 24h; Carry out forging of foundry goods after the annealing, forging temperature is 1000 ~ 800 ℃, forges into 10mm * 80mm * 90mm; To carry out the line cutting then, cut into the sample of 1mm * 10mm * 90mm.Adopt the flexural deformation method to measure its SME on the sample of well cutting, as shown in Figure 1, as can be seen from Figure 1, the shape memory response rate is between 52% ~ 41%.

Claims (2)

1. spiegel iron base marmem is characterized by: Mn 16wt%, and Si 3 ~ 5wt%, Ni 5wt%, C 0.1wt%, compound rare-earth additive 0.4 ~ 1.0 wt%, all the other are Fe; The compound rare-earth additive component is: Nd 20~28wt%, La 8~15wt%, Y 5~10wt%, Sc 4~8wt%, Ce+Pr+Eu+Gd+Tb+Ho+Er+Tm+Lu are 10~18wt%, V 2~6wt%, B 2~5wt%, Yu Weitie; In medium-frequency induction furnace, melt after the alloy preparation, when the alloy liquid temp reached 1560 ~ 1580 ℃, insulation was left standstill 3 ~ 4 minutes, when the alloy liquid temp is 1530 ~ 1550 ℃, poured into the ingot casting of Φ 80 * 150mm after skimming; The ingot casting that cast is good is put into chamber type electric resistance furnace to anneal, and purpose is to eliminate in the casting process of cooling because the internal stress that causes of cooling conditions inequality everywhere; Avoid in follow-up hot procedure, ftractureing, annealing temperature is 1080 ~ 1120 ℃, and the time is 24h; Carry out forging of foundry goods after the annealing, forging temperature is 1000 ~ 800 ℃, forges into 10mm * 80mm * 90mm; To carry out the line cutting then, cut into the sample of 1mm * 10mm * 90mm; Adopt the flexural deformation method to measure its shape memory response rate on the sample of well cutting.
2. according to the said a kind of spiegel iron base marmem of claim 1, Mn 16wt%, Si 5wt%, Ni 5wt%; C 0.10wt%, compound rare-earth additive 0.6 wt%, all the other are Fe; Dependent variable is 3% o'clock, and the shape memory response rate of alloy is the highest, and the shape memory response rate is 52%.
CN 201210329565 2012-09-08 2012-09-08 Low-manganese iron-based shape memory alloy Expired - Fee Related CN102796954B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104342596A (en) * 2013-08-09 2015-02-11 镇江忆诺唯记忆合金有限公司 Quenching technology method capable of improving memory performance of low-ferromanganese base alloy
CN105087858A (en) * 2014-05-11 2015-11-25 镇江忆诺唯记忆合金有限公司 Acidic composite rare earth alterant for smelting in electric arc furnace
CN105377472A (en) * 2013-07-10 2016-03-02 蒂森克虏伯钢铁欧洲股份公司 Method for producing a flat product from an iron-based shape memory alloy
CN105586525A (en) * 2014-10-22 2016-05-18 镇江忆诺唯记忆合金有限公司 Composite rare earth modifier for raising thermal fatigue property of heat-resistant alloy steel
CN110983152A (en) * 2019-12-27 2020-04-10 燕山大学 Fe-Mn-Si-Cr-Ni based shape memory alloy and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61284551A (en) * 1985-06-10 1986-12-15 Seiko Epson Corp Permanent magnet alloy
CN1521286A (en) * 2003-01-29 2004-08-18 上海交通大学 Rare earth modified FeMnSiCr shape memory alloy and preparation method thereof
CN101215678A (en) * 2008-01-17 2008-07-09 四川大学 Training-free casting iron-base shape memory alloy containing high temperature ferrite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61284551A (en) * 1985-06-10 1986-12-15 Seiko Epson Corp Permanent magnet alloy
CN1521286A (en) * 2003-01-29 2004-08-18 上海交通大学 Rare earth modified FeMnSiCr shape memory alloy and preparation method thereof
CN101215678A (en) * 2008-01-17 2008-07-09 四川大学 Training-free casting iron-base shape memory alloy containing high temperature ferrite

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105377472A (en) * 2013-07-10 2016-03-02 蒂森克虏伯钢铁欧洲股份公司 Method for producing a flat product from an iron-based shape memory alloy
US10450624B2 (en) 2013-07-10 2019-10-22 Thyssenkrupp Steel Europe Ag Method for producing a flat product from an iron-based shape memory alloy
CN104342596A (en) * 2013-08-09 2015-02-11 镇江忆诺唯记忆合金有限公司 Quenching technology method capable of improving memory performance of low-ferromanganese base alloy
CN105087858A (en) * 2014-05-11 2015-11-25 镇江忆诺唯记忆合金有限公司 Acidic composite rare earth alterant for smelting in electric arc furnace
CN105586525A (en) * 2014-10-22 2016-05-18 镇江忆诺唯记忆合金有限公司 Composite rare earth modifier for raising thermal fatigue property of heat-resistant alloy steel
CN110983152A (en) * 2019-12-27 2020-04-10 燕山大学 Fe-Mn-Si-Cr-Ni based shape memory alloy and preparation method thereof

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