CN1098371C - Rare earth-iron based high-temp. marmem - Google Patents
Rare earth-iron based high-temp. marmem Download PDFInfo
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- CN1098371C CN1098371C CN99116931A CN99116931A CN1098371C CN 1098371 C CN1098371 C CN 1098371C CN 99116931 A CN99116931 A CN 99116931A CN 99116931 A CN99116931 A CN 99116931A CN 1098371 C CN1098371 C CN 1098371C
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- shape memory
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Abstract
The present invention relates to rare earth iron-based shape memory alloy with high temperature, which comprises Mn, Si , Fe and other main alloy elements. The rare earth iron-based shape memory alloy has the component combination: 15 to 35 wt% of Mn, 2 to 8 wt% of Si, 2 to 8 wt% of Cr, 0.05 to 0.3 wt% of rare earth (cerium, lanthanum or misch metal) and the balance of Fe. When the Mn is firstly determined, the corresponding Si value is determined within the adoption range of the Si according to the determined Mn value. The rare earth iron-based shape memory alloy has the advantages that the shape memory effect is over 60%, the machining property is good, and the low cost is obviously lower than that of other shape memory alloy containing Ni.
Description
The present invention relates to a kind of component and melting technology thereof of shape memory alloy, especially a kind of component and melting technology thereof that can be used for the rare earth-iron based high-temp shape memory alloy of high temperature action sensor more than 250 ℃ belongs to the shape memory alloy field in the metallurgy profession.
In the iron-base marmem of prior art, contain with main alloy element such as Mn, Si and Fe, usually all determine the elemental composition selected for use with its use occasion and requirement different, be mainly used in tube stub and fastening piece, still find no the interpolation rare earth through the Searches of Patent Literature and be made into the iron-base marmem that can be used for temperature action more than 250 ℃.As:
Chinese patent application number is 92100414.1 low nickel chromium triangles, Fe-Mn-Si Series shape memory alloy, the component of its alloy is (weight percent): Mn:22～28 Si:2.5～5 C:0.02～0.06 Ni:1～3.5Cr:0.8～4, the total amount 2.3～5 of Ni and Cr.Put down in writing " being used for fastening piece and temperature-sensing element " in this patent application document.
And for example: Chinese patent application number is 91111423.8 iron-based rare-earth mamems, then propose not contain Ni, Cr, but the iron-based rare-earth shape memory alloy that contains Al, its composition range is (weight percent): Mn:15～35 Si:0.2～6.5 Cr:0.5～3 Al:0.2～8 C:＜0.9 and rare-earth elements La, and Ce, Pr, Pm...... wait one or more, content is 0.008～0.09.
In the above-mentioned technology, can be used for temperature-sensing element though number of patent application is 92100414.1 technology, use temperature is lower, A
fOnly be smaller or equal to 140 ℃, be not suitable for the high temperature action; Number of patent application is that 91111423.8 technology are mainly used in tube stub, and fails to act on temperature-sensing element.
The objective of the invention is to overcome deficiency of the prior art, a kind of component and melting technology thereof that can be used for the rare earth-iron based high-temp shape memory alloy of high temperature action Application Areas more than 250 ℃ is provided.
Technical scheme of the present invention and embodiment are as follows:
FeMnSi base alloy shape memory effect mainly is by stress-induced martensite phase transformation fcc (γ austenite) → hcp (ε martensite), by the propagation of partial dislocation with move, produces warpage.When heating, partial dislocation inverse motion, martensite reverse and become austenite, thereby make the material that was out of shape return back to original shape.The key that improves this class shape memory effect is:
1) reduces austenitic stacking fault energy, partial dislocation is moved easily;
2) strengthen austenite, make perfect dislocation be difficult for moving, thereby avoid expendable tension set;
3) avoid Neel temperature TN (antiferromagnetic phase transformation temperature) to be higher than ε martensite transformation temperature Ms.
Therefore, the alloying element scope reason that sets is: Mn is the most basic alloying element, and it has fcc → hcp phase transformation, and the scope of austenite phase in the expansion iron, reduce the Ms point, make alloy at room temperature be austenitic state, so that the matrix of stress-induced martensite to be provided.Simultaneously, Mn has the austenitic effect of solution strengthening, so its content must not be lower than 15% weight percent (in this content, easily form α ' martensite, rather than ε martensite), but the Mn too high levels will cause processing characteristics to worsen, simultaneously T
NTemperature raises, and the infringement shape memory effect is so Mn content should not be higher than 35% weight percent.
Si reduces the austenite stacking fault energy, and reduces T
NThe point.Promote the stress-induced martensite phase transformation, improve the Ms point.Simultaneously Si also plays the solution strengthening effect, so Si content should not be lower than 2% weight percent, but when Si content during greater than 8% weight percent, cold and hot working performance rapid deterioration.The content of Si and Mn needs rational Match to select for use, promptly determined Mn after, determine corresponding Si value in the scope selecting for use of Si, to regulate appropriate transformation temperature, this is to improving shape memory effect very important (seeing table 1).
Cr improves antioxidant property, simultaneously the solution strengthening effect is arranged also, but Cr improves stacking fault energy, dwindles the γ phase region.Too high levels easily forms the σ phase, causes fragility.The present invention requires not lie in to increase substantially corrosion resistance, but under atmospheric condition enough solidity to corrosions is arranged.Therefore, the Cr upper content limit is preferably 8% weight percent.
The adding of rare earth element can purify crystal boundary, and refine austenite crystal grain helps the reinforcement of parent phase; It reduces stacking fault energy simultaneously, and it is martensitic stress-induced to help ε, improves transformation temperature; More than effect not only improves hot workability, also helps improving recovery of shape temperature and shape memory effect simultaneously, and controlled contents is 0.05～0.5% weight percent.
Therefore, in order to realize purpose of the present invention, reach effect of the present invention, recipe ingredient of the present invention is weight percentage:
Mn:15～35, Si:2～8, Cr:2～8, rare earth 0.05～0.3, surplus is Fe, after Mn determines, according to determined Mn value, determines corresponding Si value in the scope selecting for use of Si.
Its melting and complete processing are as follows:
Adopt vacuum or antivacuum medium-frequency induction furnace melting, ingot casting was handled 6～8 hours through 1000～1250 ℃ of homogenizing, make the driving element of the shape that requires after 800～1200 ℃ of hot-work through cold working or cold deformation, handle through 500～1000 ℃ of typings again and get final product, make it distortion earlier in room temperature during use, when being heated to A
fThe above temperature of point, the shape in the time of can automatically returning to setting.
The present invention has substantive distinguishing features and marked improvement, and without training, single shape memory response rate reaches more than 60%, and processing characteristics is good, A
fTemperature is greater than 250 ℃, and cost is starkly lower than other and contains the Ni shape memory alloy.
Below be described further combined with example (referring to table 1):
Adopt vacuum induction melting to obtain alloy cast ingot, ingot casting is handled through 8 hours cold homogenizing of carrying out of stove of 1100 ℃ of insulations, through forge hot be rolled into φ 8.5mm bar, become φ 2mm silk material, the long tension specimen of intercepting 150mm again with hot-drawn through swaging, through 700～1000 ℃ of quenchings, at room temperature tensile, predeformation amount is 2.7～3% then, again through 600 ℃ of heating, measure its shape memory effect, also list in the table 1.◇ represent the recovery of shape rate greater than 75%, zero expression recovery of shape rate greater than 60%.Also be listed as in the table and compared processing characteristics, ◆ the expression processing characteristics is good, ● the expression processing characteristics is good.
The chemical ingredients of table 1 tested alloys (weight percent), shape memory effect and processing characteristics
| Embodiment | Mn％ | Si％ | Cr％ | Rare earth % | Fe％ | The shape memory response rate | Processing characteristics |
| 1 | 34.5 | 6.4 | 5.3 | 0.10 | Surplus | ○ | ● |
| 2 | 15.3 | 5.8 | 5.0 | 0.15 | Surplus | ○ | ◆ |
| 3 | 30.4 | 7.5 | 4.9 | 0.12 | Surplus | ◇ | ● |
| 4 | 26.0 | 2.3 | 5.1 | 0.18 | Surplus | ○ | ◆ |
| 5 | 27.1 | 6.1 | 7.7 | 0.20 | Surplus | ◇ | ◆ |
| 6 | 28.0 | 5.9 | 2.2 | 0.08 | Surplus | ◇ | ◆ |
| 7 | 26.5 | 6.0 | 5.2 | 0.25 | Surplus | ◇ | ◆ |
| 8 | 27.4 | 5.4 | 5.2 | 0.06 | Surplus | ○ | ◆ |
No. 7 alloys are made extension spring, (line footpath d=2mm, spring inside diameter D
In=8mm, number of active coils n=8)
1). under 20 ℃ of constant temperature, rate of extension is 5.0mm/min.Measure its load-deformation characteristic curve.Unload after spring is stretched to 27.3mm, and load reaches 110N, the residual elongation amount is 15.6mm.
2) heat under the condition that keeps elongation 15.6mm, (heating rate: 7 ℃/min), the result shows that the restoring force of spring generation reaches 59N when temperature to 280 ℃ to the load in the measuring spring recovery of shape process---temperature characteristics.When being heated to 320 ℃, load no longer increases after reaching 60N.The spring that this alloy is made has been tried out in fire-protection valve (requiring 280 ℃ of actions), and the more existing stainless die shape memory spring of effect is much better, and latter's operating temperature is less than 200 ℃, and shape memory effect decline easily after thermal cycling.
Claims (2)
1, a kind of rare earth-iron based high-temp shape memory alloy, contain Mn, Si and Fe main alloy element, it is characterized in that the recipe ingredient weight percent is: Mn: 15～35, Si: 2～8, Cr: 2～8, rare earth 0.05～0.3, surplus is Fe, after Mn determines earlier,, determine corresponding Si value in the scope selecting for use of Si according to determined Mn value.
2, the melting technology of rare earth-iron based high-temp shape memory alloy according to claim 1, it is characterized in that its melting technology is as follows: adopt vacuum or antivacuum medium-frequency induction furnace melting, ingot casting is through 1000～1250 ℃ of even processing 6～8 hours, 800～1200 ℃ of hot-work.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116931A CN1098371C (en) | 1999-09-30 | 1999-09-30 | Rare earth-iron based high-temp. marmem |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116931A CN1098371C (en) | 1999-09-30 | 1999-09-30 | Rare earth-iron based high-temp. marmem |
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| Publication Number | Publication Date |
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| CN1249356A CN1249356A (en) | 2000-04-05 |
| CN1098371C true CN1098371C (en) | 2003-01-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99116931A Expired - Fee Related CN1098371C (en) | 1999-09-30 | 1999-09-30 | Rare earth-iron based high-temp. marmem |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128244C (en) * | 2000-10-26 | 2003-11-19 | 艾默生电气（中国）投资有限公司 | Fe-Mn-Si base marmem containing Cr and N and its training method |
| US20130160900A1 (en) * | 2011-12-22 | 2013-06-27 | Airbus Engineering Centre India | SHAPE MEMORY STAINLESS STEELS WITH RARE EARTH ELEMENTS Ce AND La |
| CN104342538A (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 high-ferromanganese base 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 |
| CN113802030A (en) * | 2021-10-14 | 2021-12-17 | 上海交通大学 | Rare earth high-temperature alloy construction material and ultralimit precision casting method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181425A (en) * | 1997-10-20 | 1998-05-13 | 河北工业大学 | Making method of iron-base marmem pipe joint |
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1999
- 1999-09-30 CN CN99116931A patent/CN1098371C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181425A (en) * | 1997-10-20 | 1998-05-13 | 河北工业大学 | Making method of iron-base marmem pipe joint |
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| CN1249356A (en) | 2000-04-05 |
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