CN102758097A - Low-aluminium high-manganese CuAlMn low-temperature memory alloy - Google Patents
Low-aluminium high-manganese CuAlMn low-temperature memory alloy Download PDFInfo
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Abstract
The invention discloses a low-aluminium high-manganese CuAlMn low-temperature memory alloy and belongs to the technical field of memory alloys. The alloy is characterized in that a material which comprises 14-16 wt.% of Al, 8-9 wt.% of Mn, 0.3-0.8 wt.% of a composite rare earth additive and the balance copper is smelted in an electric vacuum induction furnace. The alloy is smelted and cast into a cast ingot with the diameter of phi80*150mm, annealing treatment is conducted, turning is conducted to remove a surface by 2-3mm, the cast ingot is forged into a bar of 30*30mm, extruded into a wire rod of phi4mm and then subjected to cold-drawing to form a wire of phi0.5-2mm, and finally, vacuum heat treatment is conducted. At this moment, the martensite transformation temperature of the low-aluminium high-manganese CuAlMn low-temperature memory alloy is in a range of 100-180K, and the reverse martensite transformation temperature is in a range of 120-200K.
Description
Technical field
The invention belongs to the memorial alloy technical field, refer in particular to the high manganese CuAlMn of a kind of low aluminium low temperature memorial alloy.
Background technology
Discovering in recent years, CuAlMn is a kind of memorial alloy with better low temperature SME.Up to the present, report is considerably less both at home and abroad for the relevant shape memory alloy of martensitic transformation temperature Ms below 200 K.Subzero valve (working temperature is lower than the valve of 200K) is one of industrial indispensable visual plants such as petrochemical complex, air separation, Sweet natural gas, can the quality of its quality is determining safely, economical, produce constantly.The Subzero valve working conditions is harsh, and its working medium major part is the material inflammable, explosive, that perviousness is strong, and minimum operating temperature can reach 4K, and extreme service presure reaches 10MPa.The liquid nitrogen bottle that in utilizing the device of liquid nitrogen refrigerating, uses at present all has certain slit; Even when environment on every side reaches needed low temperature; Liquid nitrogen in the liquid nitrogen bottle also still continues to outflow; So in the refrigerating working process, cause the very big waste of liquid nitrogen, and also reduced the working hour of refrigeration plant.CuAlMn low temperature memorial alloy can be applied in ultra-low temperature surroundings, like the Working environment under the liquid nitrogen temperature.Make a temperature controlling valve if utilize this alloy; It is opened the liquid nitrogen bottleneck when high temperature automatically, discharge liquid nitrogen refrigerating, when temperature is reduced to needed low temperature, close bottleneck automatically again; So just can reduce the flow of liquid nitrogen in the cryogenic system; Thereby can reduce the consumption of liquid nitrogen effectively, prolong the working hour of refrigeration plant, reach the purpose of save energy.But Mn can volatilize in the preparation process of alloy and heat treatment process; This makes the composition of CuAlMn alloy, and all great changes will take place before and after vacuum metling and vacuum heat treatment; And the volatilization situation of Mn is also inequality after each different heat treatment; Therefore be difficult to obtain the alloy consistent with design mix, it is then difficult especially to expect that ideal has a shape memory alloy of low-temperature martensitic transformation temperature.For the high manganese CuAlMn of low aluminium low temperature memorial alloy, except the volatilization that will reduce Mn, also to improve because the add-on of Mn increases the problem that causes alloy toughness to descend.The present invention develops the high manganese CuAlMn of a kind of low aluminium low temperature memorial alloy.
Summary of the invention
The objective of the invention is to develop the high manganese CuAlMn of a kind of low aluminium low temperature memorial alloy, it is characterized by: with composition is Al14～16wt%, Mn8～9wt%, and compound rare-earth additive 0.3～0.8wt%, all the other carry out melting for the material of copper in vacuum induction furnace.Compound rare-earth additive chemistry composition is: Y 20～28wt%, La 8～15wt%, Ce5～12wt%, Nb+Pr+Eu+Gd+Tb+Ho+Er+Tm+Lu are 10～18wt%, V2～6wt%, B2～5wt%, Zr2～5wt%, Yu Weitong.It is bulk alloy that said compound rare-earth adds agent, 800～1200 ℃ of melting ranges.When the alloy liquid temp reached 1280～1300 ℃, 5min was left standstill in insulation, in vacuum induction furnace, pours into the ingot casting that diameter is φ 80 * 150mm then behind the alloy melting.Carry out anneal after the ingot casting cooling; Anneal is to be heated to 840 ℃ of insulations furnace cooling after 24 hours, and surface 2～3mm is removed in turning processing then, forges the bar to 30 * 30mm; Forge 800～840 ℃ of temperature; Be squeezed into the wire rod of Φ 4mm again, 650～680 ℃ of extrusion temperatures, last cold-drawn becomes the silk material of Ф 0.5～2mm.Carry out vacuum heat treatment then, its concrete technology is: 860 ℃ of insulations are quenched after 30 minutes in the room temperature oil, carry out (being incubated 30 minutes) in 170 ℃ of oil again and 100 ℃ of water in three grades of ageing treatment of (being incubated 15 minutes) in (being incubated 15 minutes) and the 50 ℃ of water.Utilize the high manganese CuAlMn of the low aluminium low temperature memory alloy wire material that obtains, can be used for field of engineering technology, its concrete size can be confirmed according to the actual requirement of using.This moment, the martensite transformation temperature of the low high manganese CuAlMn of aluminium low temperature memorial alloy was 100～180K, and contrary martensite transformation temperature is 120～200K, and the mechanical property of alloy is σ
b=572MPa～578MPa, σ
0.2=291MPa～296MPa, δ=18.1～19.5%.Because the adding of compound rare-earth additive effectively prevents the volatilization of Mn, and makes alloy have good toughness.Manganese content can't prepare the wire vent material later on greater than 9wt%, does not have using value.The compound rare-earth additive greater than 0.8wt% after, the mechanical property of alloy is descended, also cause preparing the wire vent material.
Embodiment
Embodiment 1:
The low high manganese CuAlMn of the aluminium low temperature memorial alloy of preparation is Al14wt% with chemical ingredients, Mn8wt%, and compound rare-earth additive 0.3wt%, all the other carry out melting for the material of copper in vacuum induction furnace.When the alloy liquid temp reached 1280～1300 ℃, 5min was left standstill in insulation, in vacuum induction furnace, pours into the ingot casting that diameter is φ 80 * 150mm then behind the alloy melting.Carry out anneal after the ingot casting cooling; Anneal is to be heated to 840 ℃ of insulations furnace cooling after 24 hours, and surface 2～3mm is removed in turning processing then, forges the bar to 30 * 30mm; Forge 800～840 ℃ of temperature; Be squeezed into the wire rod of Φ 4mm again, 650～680 ℃ of extrusion temperatures, last cold-drawn becomes the silk material of Ф 0.5～2mm.Carry out vacuum heat treatment then, its concrete technology is: 860 ℃ of insulations are quenched after 30 minutes in the room temperature oil, carry out (being incubated 30 minutes) in 170 ℃ of oil again and 100 ℃ of water in three grades of ageing treatment of (being incubated 15 minutes) in (being incubated 15 minutes) and the 50 ℃ of water.Utilize the high manganese CuAlMn of the low aluminium low temperature memory alloy wire material that obtains, can be used for field of engineering technology, its concrete size can be confirmed according to the actual requirement of using.This moment, the low high manganese CuAlMn of aluminium low temperature memorial alloy composition was Al13.992wt%, Mn7.962wt%, and compound rare-earth 0.291wt%, surplus is a copper, and martensite transformation temperature is 180K ± 3K, and contrary martensite transformation temperature is 200K ± 3K, and the mechanical property of alloy is σ
b=572MPa, σ
0.2=291MPa, δ=18.1%.
Embodiment 2:
The low high manganese CuAlMn of the aluminium low temperature memorial alloy of preparation is Al15wt% with chemical ingredients, Mn8.5wt%, and compound rare-earth additive 0.8wt%, all the other carry out melting for the material of copper in vacuum induction furnace.When the alloy liquid temp reached 1280～1300 ℃, 5min was left standstill in insulation, in vacuum induction furnace, pours into the ingot casting that diameter is φ 80 * 150mm then behind the alloy melting.Carry out anneal after the ingot casting cooling; Anneal is to be heated to 840 ℃ of insulations furnace cooling after 24 hours, and surface 2～3mm is removed in turning processing then, forges the bar to 30 * 30mm; Forge 800～840 ℃ of temperature; Be squeezed into the wire rod of Φ 4mm again, 650～680 ℃ of extrusion temperatures, last cold-drawn becomes the silk material of Ф 0.5～2mm.Carry out vacuum heat treatment then, its concrete technology is: 860 ℃ of insulations are quenched after 30 minutes in the room temperature oil, carry out (being incubated 30 minutes) in 170 ℃ of oil again and 100 ℃ of water in three grades of ageing treatment of (being incubated 15 minutes) in (being incubated 15 minutes) and the 50 ℃ of water.Utilize the high manganese CuAlMn of the low aluminium low temperature memory alloy wire material that obtains, can be used for field of engineering technology, its concrete size can be confirmed according to the actual requirement of using.This moment, the low high manganese CuAlMn of aluminium low temperature memorial alloy composition was Al14.993wt%, Mn8.464wt%, and compound rare-earth 0.792wt%, surplus is a copper, and martensite transformation temperature is 140K ± 3K, and contrary martensite transformation temperature is 160K ± 3K, and the mechanical property of alloy is σ
b=574MPa, σ
0.2=293MPa, δ=18.7%.
Embodiment 3:
The low high manganese CuAlMn of the aluminium low temperature memorial alloy of preparation is Al16wt% with chemical ingredients, Mn9wt%, and compound rare-earth additive 0.6wt%, all the other carry out melting for the material of copper in vacuum induction furnace.When the alloy liquid temp reached 1280～1300 ℃, 5min was left standstill in insulation, in vacuum induction furnace, pours into the ingot casting that diameter is φ 80 * 150mm then behind the alloy melting.Carry out anneal after the ingot casting cooling; Anneal is to be heated to 840 ℃ of insulations furnace cooling after 24 hours, and surface 2～3mm is removed in turning processing then, forges the bar to 30 * 30mm; Forge 800～840 ℃ of temperature; Be squeezed into the wire rod of Φ 4mm again, 650～680 ℃ of extrusion temperatures, last cold-drawn becomes the silk material of Ф 0.5～2mm.Carry out vacuum heat treatment then, its concrete technology is: 860 ℃ of insulations are quenched after 30 minutes in the room temperature oil, carry out (being incubated 30 minutes) in 170 ℃ of oil again and 100 ℃ of water in three grades of ageing treatment of (being incubated 15 minutes) in (being incubated 15 minutes) and the 50 ℃ of water.Utilize the high manganese CuAlMn of the low aluminium low temperature memory alloy wire material that obtains, can be used for field of engineering technology, its concrete size can be confirmed according to the actual requirement of using.This moment, CuAlMn low temperature memorial alloy composition was Al15.492wt%, Mn8.967wt%, and compound rare-earth 0.592wt%, surplus is a copper.Martensite transformation temperature is 100K ± 3K, and contrary martensite transformation temperature is 120K ± 3K, and the mechanical property of alloy is σ
b=578MPa, σ
0.2=296MPa, δ=19.5%.
Comparative Examples:
The low high manganese CuAlMn of the aluminium low temperature memorial alloy of preparation is Al16wt% with chemical ingredients, Mn9wt%, and all the other carry out melting for the material of copper in vacuum induction furnace.When the alloy liquid temp reached 1280～1300 ℃, 5min was left standstill in insulation, in vacuum induction furnace, pours into the ingot casting that diameter is φ 80 * 150mm then after the melting.Carry out anneal after the ingot casting cooling; Anneal is to be heated to 840 ℃ of insulations furnace cooling after 24 hours, and surface 2～3mm is removed in turning processing then, forges the bar to 30 * 30mm; Forge 800～840 ℃ of temperature; Be squeezed into the wire rod of Φ 4mm again, 650～680 ℃ of extrusion temperatures, last cold-drawn becomes the silk material of Ф 0.5～2mm.Carry out vacuum heat treatment then, its concrete technology is: 860 ℃ of insulations are quenched after 30 minutes in the room temperature oil, carry out (being incubated 30 minutes) in 170 ℃ of oil again and 100 ℃ of water in three grades of ageing treatment of (being incubated 15 minutes) in (being incubated 15 minutes) and the 50 ℃ of water.Utilize the high manganese CuAlMn of the low aluminium low temperature memory alloy wire material that obtains, can be used for field of engineering technology, its concrete size can be confirmed according to the actual requirement of using.This moment, CuAlMn low temperature memorial alloy composition was Al15.492wt%, Mn8.61wt%, and surplus is a copper.Martensite transformation temperature is 150K ± 3K, and contrary martensite transformation temperature is 170K ± 3K, and the mechanical property of alloy is σ
b=563MPa, σ
0.2=286MPa, δ=14.7%.
Claims (2)
1. the high manganese CuAlMn of low aluminium low temperature memorial alloy, it is characterized by: with composition is Al14～16wt%, Mn8～9wt%, compound rare-earth additive 0.3～0.8wt%, all the other carry out melting for the material of copper in vacuum induction furnace; Compound rare-earth additive chemistry composition is: Y 20～28wt%, La 8～15wt%, Ce5～12wt%, Nb+Pr+Eu+Gd+Tb+Ho+Er+Tm+Lu are 10～18wt%, V2～6wt%, B2～5wt%, Zr2～5wt%, Yu Weitong; It is bulk alloy that said compound rare-earth adds agent, 800～1200 ℃ of melting ranges; When the alloy liquid temp reached 1280～1300 ℃, 5min was left standstill in insulation, in vacuum induction furnace, pours into the ingot casting that diameter is φ 80 * 150mm then behind the alloy melting; Carry out anneal after the ingot casting cooling; Anneal is to be heated to 840 ℃ of insulations furnace cooling after 24 hours, and surface 2～3mm is removed in turning processing then, forges the bar to 30 * 30mm; Forge 800～840 ℃ of temperature; Be squeezed into the wire rod of Φ 4mm again, 650～680 ℃ of extrusion temperatures, last cold-drawn becomes the silk material of Ф 0.5～2mm; Carry out vacuum heat treatment then, its concrete technology is: 860 ℃ of insulations are quenched after 30 minutes in the room temperature oil, carry out (being incubated 30 minutes) in 170 ℃ of oil again and 100 ℃ of water in three grades of ageing treatment of (being incubated 15 minutes) in (being incubated 15 minutes) and the 50 ℃ of water; Utilize the high manganese CuAlMn of the low aluminium low temperature memory alloy wire material that obtains, can be used for field of engineering technology, its concrete size can be confirmed according to the actual requirement of using; This moment, the martensite transformation temperature of the low high manganese CuAlMn of aluminium low temperature memorial alloy was 100～180K, and contrary martensite transformation temperature is 120～200K, and the mechanical property of alloy is σ
b=572MPa～578MPa, σ
0.2=291MPa～296MPa, δ=18.1～19.5%; Because the adding of compound rare-earth additive effectively prevents the volatilization of Mn, and makes alloy have good toughness.
2. according to the high manganese CuAlMn of the said a kind of low aluminium of claim 1 low temperature memorial alloy, as being divided into Al16 wt%, Mn9wt%, compound rare-earth additive 0.6wt%, surplus is that copper is when carrying out the vacuum induction furnace melting and preparing the low temperature memorial alloy; This moment, CuAlMn low temperature memorial alloy composition was Al15.492wt%; Mn8.967wt%, compound rare-earth 0.592wt%, martensite transformation temperature are 100K ± 3K; Contrary martensite transformation temperature is 120K ± 3K, and the mechanical property of alloy is σ
b=578MPa, σ
0.2=296MPa, δ=19.5%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102952982A (en) * | 2012-11-20 | 2013-03-06 | 无锡常安通用金属制品有限公司 | Low-temperature memory alloy and preparation method of low-temperature memory alloy |
| CN102952980A (en) * | 2012-11-20 | 2013-03-06 | 无锡常安通用金属制品有限公司 | Wide-temperature range memory alloy and preparation method thereof |
| CN102969113A (en) * | 2012-11-20 | 2013-03-13 | 无锡常安通用金属制品有限公司 | Hard magnetic alloy and preparation thereof |
| CN103421981A (en) * | 2013-08-08 | 2013-12-04 | 常熟市东方特种金属材料厂 | High-damping shape memory alloy |
| CN104342577A (en) * | 2013-08-04 | 2015-02-11 | 镇江忆诺唯记忆合金有限公司 | Copper zinc aluminum memory alloy capable of improving hardness stability under hot and cold cycling |
| CN105088003A (en) * | 2014-05-07 | 2015-11-25 | 镇江忆诺唯记忆合金有限公司 | Copper-aluminum-iron-nickel-manganese alloy capable of improving mechanical properties |
| CN105088002A (en) * | 2014-05-07 | 2015-11-25 | 镇江忆诺唯记忆合金有限公司 | Copper-aluminum-iron-nickel-manganese-tungsten-molybdenum alloy with improved thermal fatigue resistant property |
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| CN101956095A (en) * | 2010-10-15 | 2011-01-26 | 镇江忆诺唯记忆合金有限公司 | CuAlMn low-temperature memory alloy spring |
| CN102021465A (en) * | 2010-10-15 | 2011-04-20 | 镇江忆诺唯记忆合金有限公司 | Composite rare earth addictive for preventing Mn in CuAlMn memory alloy from volatilizing |
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Patent Citations (2)
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| CN101956095A (en) * | 2010-10-15 | 2011-01-26 | 镇江忆诺唯记忆合金有限公司 | CuAlMn low-temperature memory alloy spring |
| CN102021465A (en) * | 2010-10-15 | 2011-04-20 | 镇江忆诺唯记忆合金有限公司 | Composite rare earth addictive for preventing Mn in CuAlMn memory alloy from volatilizing |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952982A (en) * | 2012-11-20 | 2013-03-06 | 无锡常安通用金属制品有限公司 | Low-temperature memory alloy and preparation method of low-temperature memory alloy |
| CN102952980A (en) * | 2012-11-20 | 2013-03-06 | 无锡常安通用金属制品有限公司 | Wide-temperature range memory alloy and preparation method thereof |
| CN102969113A (en) * | 2012-11-20 | 2013-03-13 | 无锡常安通用金属制品有限公司 | Hard magnetic alloy and preparation thereof |
| CN102969113B (en) * | 2012-11-20 | 2015-12-02 | 江苏高博智融科技有限公司 | A kind of hard magnetic alloy and preparation thereof |
| CN104342577A (en) * | 2013-08-04 | 2015-02-11 | 镇江忆诺唯记忆合金有限公司 | Copper zinc aluminum memory alloy capable of improving hardness stability under hot and cold cycling |
| CN103421981A (en) * | 2013-08-08 | 2013-12-04 | 常熟市东方特种金属材料厂 | High-damping shape memory alloy |
| CN105088003A (en) * | 2014-05-07 | 2015-11-25 | 镇江忆诺唯记忆合金有限公司 | Copper-aluminum-iron-nickel-manganese alloy capable of improving mechanical properties |
| CN105088002A (en) * | 2014-05-07 | 2015-11-25 | 镇江忆诺唯记忆合金有限公司 | Copper-aluminum-iron-nickel-manganese-tungsten-molybdenum alloy with improved thermal fatigue resistant property |
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Effective date of registration: 20151207 Address after: 518000, Shenzhen, Guangdong, Nanshan District, Nantou, Shennan Avenue and former sea, southeast corner coast times apartment west room 1105 Patentee after: Shenzhen Minglida Precision Machinery Co., Ltd. Address before: 212009 Zhenjiang City, Jiangsu Province Siping Road Economic Development Zone No. 5 Ze Xing Branch Patentee before: Yinuowei Shape Memory Alloys Co., Ltd., Zhenjiang |
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Address after: 518000 floor 4, Qinghua Information Port scientific research building, west side of South Gate, No. 13, Langshan Road, songpingshan community, Xili street, Nanshan District, Shenzhen City, Guangdong Province Patentee after: Shenzhen minglida Precision Technology Co., Ltd Address before: 518000, Shenzhen, Guangdong, Nanshan District, Nantou, Shennan Avenue and former sea, southeast corner coast times apartment west room 1105 Patentee before: SHENZHEN MINGLIDA PRECISION MACHINERY Co.,Ltd. |