CN100535148C - Manganese-based memory alloy with high-strength, plasticity and damping performances and production thereof - Google Patents
Manganese-based memory alloy with high-strength, plasticity and damping performances and production thereof Download PDFInfo
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- CN100535148C CN100535148C CNB2006100387787A CN200610038778A CN100535148C CN 100535148 C CN100535148 C CN 100535148C CN B2006100387787 A CNB2006100387787 A CN B2006100387787A CN 200610038778 A CN200610038778 A CN 200610038778A CN 100535148 C CN100535148 C CN 100535148C
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- memorial alloy
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Abstract
The invention provided a high strength, plasticity and damping Mangonic. It is proper to make the propeller of the naval vessels and the ship craft, the anti-chatter bushing, the muffler shell, the memory function parts, glass frame, the medical silk guide, surgical sutures. The weight ratio of the composition is Cu 5.5-50%, Ni 1-10%, Cr 1-10%, N 0.05-0.5%, the residue is Mn. The alloy smelt to cast ingot by the median or high frequency atmospheric casting in the ceramic crucible, argon shield or the magnetic suspension smelting and the Ohno Continue Castings. The alloy has the high yield strength, good memory ability, hyperelastic and not easy to rustiness.
Description
Technical field:
The present invention relates to a kind of memorial alloy, especially relate to a kind of high-strength high-plasticity high damping manganese base memorial alloy and preparation method thereof.Be specially adapted to manufacture water screw, antidetonation bearing shell, the muffler shell of naval vessels, boats and ships; Memory function is part in addition, as the sensor of temperature and power, spectacle frame, medical guiding wire, surgical sutures or the like.
Background technology:
The seventies in 20th century, the U.S. found copper-based memory alloy successively to have occurred since the Ultimum Ti, the iron-based memorial alloy, and can practicality and industrialization.Ultimum Ti is because its good memory performance and super-elasticity is used the most successful.But its scarcity of resources, cost an arm and a leg (600～20000 yuan of per kilograms), the complex manufacturing difficulty, when being used for health care, the stripping of nickel ion is harmful; Though copper-based memory alloy price low (be Ultimum Ti price 1/5), technology is simple, aboundresources, but its fatal shortcoming is a coarse crystal, and the performance directivity is big, so grain-boundary strength is very low, easily cold conditions fracture, fatigue lifetime is very low, limits its practicality greatly; Iron-based memorial alloy aboundresources, price is lower, and structural manufacturing process is similar to stainless steel, but its memory capability very poor (be Ultimum Ti 1/4～1/5), and the one way memory capability is only arranged, also limited its application greatly.In order further to reduce price, improve the cold and hot working manufacturability, improve biocompatibility, obtain good absorbing vibration (damping) ability, be base memorial alloy so developed with manganese.But the yield strength of present manganese base memorial alloy is low, 200MPa; Memory capability is poor, reminiscence rate 30～50%; Super-elasticity is poor, and 0.5%; Easily get rusty.
Summary of the invention:
The objective of the invention is to overcome the deficiency of existing manganese base memorial alloy, high-strength high-plasticity high damping manganese base memorial alloy that provide a kind of yield strength height, memory capability is good, super-elasticity is good, is difficult for getting rusty and preparation method thereof.
The object of the present invention is achieved like this: a kind of high-strength high-plasticity high damping manganese base memorial alloy, it is characterized in that: it is basic adopting with Mn, the main Cu that is added with, be added with Ni and Cr again, the auxilliary N that is added with, the weight percent of its each component is: Cu 5.5～50%, Ni 1～10%, Cr 1～10%, N 0.05～0.5, and all the other are Mn, the summation of each component is 100%.
The present invention also can add a kind of among Ti, Sn, Sb, the Si or several in above-mentioned alloy ingredient, its dosage is: Ti 0.5～5% or/and Sn 0.1～5% or/and Sb0.1～2% or/and Si0.1～2%.
The present invention preferentially adopts Cu 25%, Ni5%, Cr3%, N0.1% and Ti1%, and all the other are Mn.Other element can add also and can not add, on to remembering super bullet and the damping requirement is decided.
Contain element N: have the interval mutually to enlarge high temperature, make dissolving Cu content expand 55% to, form interstitial solid solution simultaneously, greatly reinforced alloys and improve super-elasticity; Contain element ti and also enlarge high temperature and have the interval mutually, solid solution strengthening effect is big because atomic radius is big; Element sb, Sn, Si has same purpose, but effect is relatively poor; Element Cr, Ni content is more, reinforced alloys not only, and mainly improve alloy antibiosis rust ability.
It is too much to add N, causes the alloy internal porosity, and the method that adds N is to add melt with the master alloy form, and master alloy has NCr compound or NMn compound; Add Ti and too much cause alloy fragility; Add too much Cr, Ni, cost increases a lot, also influences the memory performance variation.
The preparation method of high-strength high-plasticity high damping manganese base memorial alloy of the present invention is characterized in that it comprises:
A) ceramic crucible intermediate frequency or the melting of high frequency atmosphere are adopted in the melting of the molten alloy of alloy, melting under the argon shield, or magnetic levitation melting acquisition ingot casting, or adopt the melting of Ohno Continue Castings technology to obtain ingot casting;
B) formation silk rod, strip section bar place ingot casting under protective atmosphere or the vacuum and made its homogenizing in 6～8 hours in 800～850 ℃ of insulations; 800～850 ℃ of beginning hot rollings; 500～550 ℃ of finish to gauges; 650～500 ℃ of thermal stretchs form the silk rod of φ 0.1～10mm, or are cold rolled to the strip section bar of 0.1～5mm.
Ohno Continue Castings is called for short OCC, by the wild professor's invention of day own job, this technology is solidifying from heart portion of ingot sample, and ingot sample outside is by forcing heating not allow a kind of hot-mold continuous cast that solidifies earlier, be a kind of zero defect, monocrystalline or cylindrulite near-net-shape technology.
Every time is 10～30% for cold rolling machining deformation amount, the process annealing temperature is 600～650 ℃, heat-up time, every gram product was 10～15 seconds, and final operation is 800 ℃～850 ℃, every gram product heat-up time cold-water quench after 10～15 seconds, handle through ageing strengthening again, 400～500 ℃ of aging temps, aging time are 2～6 hours, and be cold rolling at last, cold drawn, deflection is 30～40%.
The finished product performance that obtains with casting method is: σ
b〉=450Mpa, σ
S〉=250Mpa, δ 〉=20%, martensite is to austenitic transformation end of a period transformation temperature A
fAt 0～200 ℃, the super bullet distortion of residual set 0.5% reaches 2～4%.
With monocrystalline or column crystal material that the OCC technology obtains, the finished product performance is: tensile strength sigma
b〉=400Mpa, yield strength σ
S〉=200Mpa, unit elongation δ 〉=20%, martensite is to austenitic transformation end of a period transformation temperature A
fAt 0～200 ℃, the super bullet distortion of residual set 0.5% reaches 4～10%.
In sum, the present invention has the yield strength height, and memory capability is good, and super-elasticity is good, and characteristics such as be difficult for getting rusty.
Embodiment:
Embodiment 1
With the alloy material of the present invention that the melting of magnetic levitation high-frequency induction obtains, its composition is: 19%Cu (weight part, down together), and 3%Ni, 3%Cr, 0.1N%, 05Ti, all the other are Mn.The 1kg ingot blank places under protective atmosphere or the vacuum in 850 ℃ of homogenizing thermal treatments 6 hours; 850 ℃ of beginning hot rollings; 550 ℃ of finish to gauges become the long 300mm lath of the wide 20mm of thick 2.5mm; carry out cold rolling, cold rolling machining deformation amount every time 20%, the process annealing temperature is 600 ℃; heated 120 seconds; carry out 120 seconds ice water quenching of 800 ℃ of heating again, and through 400 ℃ of timeliness 4.5 hours, again through being cold rolled to the lath of thick 1.5mm.Record σ
b〉=750Mpa, σ
S〉=350Mpa, δ are 30%, A
f=125 ℃.
Embodiment 2
With the alloy material of the present invention that the melting of magnetic levitation high-frequency induction obtains, its composition is: 10%Cu, and 3%Ni,, 3%Cr, 0.1%N, 0.5%Ti, all the other are Mn.The 1kg ingot blank places under protective atmosphere or the vacuum in 850 ℃ of homogenizing thermal treatments 6 hours; 850 ℃ of beginning hot rollings; 550 ℃ of finish to gauges become the long 300mm lath of the wide 20mm of thick 1.5mm; carry out cold rolling, cold rolling machining deformation amount every time 20%, the process annealing temperature is 600 ℃; heated 120 seconds; carry out 120 seconds ice water quenching of 800 ℃ of heating again, after 400 ℃ of timeliness 4.5 hours, again through being cold rolled to the lath of thick 1.5mm.Record σ
b〉=550Mpa, σ
S〉=250Mpa, δ are 35%, A
f=155 ℃.
Embodiment 3
With ceramic crucible atmosphere Medium frequency induction melting alloy material of the present invention, its composition is: 35%Cu, and 5%Ni, 3%Cr, 0.1%N, 0.5Ti%, 0.1Sn%, 0.1Sb%, all the other are Mn.The 1kg ingot blank places under protective atmosphere or the vacuum in 850 ℃ of homogenizing thermal treatments 6 hours; 850 ℃ of beginning hot rollings; 550 ℃ of finish to gauges become the long 300mm lath of the wide 20mm of thick 1.5mm; carry out cold rolling, cold rolling machining deformation amount every time 20%, the process annealing temperature is 600 ℃; heated 120 seconds; proceed to 120 seconds ice water quenching of 800 ℃ of heating again, after 430 ℃ of timeliness 4 hours, again through being cold rolled to the lath of thick 1.5mm.Record σ
b〉=850Mpa, σ
S〉=450Mpa, δ are 25%, A
f=5 ℃, 18 ℃ super bullet distortion 4%, residual set 0.3%.
Embodiment 4
With the alloy material of the present invention that OCC technology continuous casting draws, its composition is: 38%Cu, and 5%Ni, 5%Cr, 0.1%N, 1%Ti, 1%Sn, 0.1%Si, all the other are Mn.The 1kg ingot blank places under protective atmosphere or the vacuum in 850 ℃ of homogenizing thermal treatments 6 hours; 850 ℃ of beginning hot rollings; 550 ℃ of finish to gauges become the long 300mm lath of the wide 20mm of thick 1.5mm; carry out cold rolling, cold rolling machining deformation amount every time 20%, the process annealing temperature is 600 ℃; heated 120 seconds; proceed to 120 seconds ice water quenching of 800 ℃ of heating again, after 450 ℃ of timeliness 4.8 hours, again through being cold rolled to the lath of thick 1.5mm.Record σ
b〉=880Mpa, σ
S〉=550Mpa, δ are 24%, A
f=0 ℃, 8 ℃ super bullet distortion 8%, residual set 0.2%.
Embodiment 5
With the alloy material of the present invention that the melting of magnetic levitation high-frequency induction obtains, its composition is: 19%Cu (weight part, down together), and 3%Ni, 3%Cr, 0.1N%, 05Ti, all the other are Mn.The 1kg ingot blank places under protective atmosphere or the vacuum in 850 ℃ of homogenizing thermal treatments 6 hours, 850 ℃ of beginning hot rollings, and 550 ℃ of finish to gauges become
The silk rod of 8mm, 650～500 ℃ are carried out thermal stretch, hot-drawn machining deformation amount every time 20%, carry out 120 seconds ice water quenching of 800 ℃ of heating again, and through 400 ℃ of timeliness 4.5 hours, again through being cold drawn to
1.5mm the silk material.Record σ
b〉=850Mpa, σ
S〉=450Mpa, δ are 20%, A
f=125 ℃.
Claims (4)
1, a kind of high-strength high-plasticity high damping manganese base memorial alloy, it is characterized in that: it is basic adopting with Mn, the main Cu that is added with, be added with Ni and Cr again, the auxilliary N that is added with, the weight percent of its each component is: Cu 5.5～50%, Ni 1～10%, Cr 1～10%, N 0.05～0.5%, and all the other are Mn, the summation of each component is 100%.
2, a kind of high-strength high-plasticity high damping manganese base memorial alloy according to claim 1, it is characterized in that: add a kind of among Ti, Sn, Sb, the Si or several in the described manganese base memorial alloy composition, its dosage is: Ti 0.5～5% or/and Sn 0.1～5% or/and Sb0.1～2% or/and Si0.1～2%.
3, a kind of high-strength high-plasticity high damping manganese base memorial alloy according to claim 2 is characterized in that: described manganese base memorial alloy composition adopts 25%Cu, 5%Ni, 3%Cr, 0.1%N and 1%Ti, and all the other are Mn.
4, the preparation method of high-strength high-plasticity high damping manganese base memorial alloy as claimed in claim 1 is characterized in that it comprises:
Ceramic crucible intermediate frequency or the melting of high frequency atmosphere are adopted in the melting of alloy, or magnetic levitation melting acquisition ingot casting,
Ingot casting placed under protective atmosphere or the vacuum in 800～850 ℃ of insulations made its homogenizing in 6～8 hours; 800～850 ℃ of beginning hot rollings; 500～550 ℃ of finish to gauges, 650～500 ℃ of thermal stretchs form the silk rod of φ 0.1～10mm, or are cold rolled to the strip section bar of 0.1～5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100387787A CN100535148C (en) | 2006-03-10 | 2006-03-10 | Manganese-based memory alloy with high-strength, plasticity and damping performances and production thereof |
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| CNB2006100387787A CN100535148C (en) | 2006-03-10 | 2006-03-10 | Manganese-based memory alloy with high-strength, plasticity and damping performances and production thereof |
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| CN100535148C true CN100535148C (en) | 2009-09-02 |
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| CN103088225B (en) * | 2012-12-21 | 2014-08-20 | 江苏中容铜业有限公司 | Preparation method of oxygen-free copper base alloy for propeller |
| CN103341520B (en) * | 2013-07-04 | 2016-03-23 | 中国科学院金属研究所 | A kind of TB9 square-section titanium alloy wire materials preparation technology |
| CN104120314A (en) * | 2014-08-12 | 2014-10-29 | 天津银龙高科新材料研究院有限公司 | High-damping MnCu alloy and powdery metallurgy preparation technology thereof |
| CN104195484A (en) * | 2014-08-20 | 2014-12-10 | 西安钢研功能材料有限责任公司 | Preparation method of Mn72Ni10Cu18 alloy strip |
| CN104451299A (en) * | 2014-11-14 | 2015-03-25 | 南昌大学 | Novel antiferromagnetic MnNiCu damping alloy and preparation method thereof |
| CN104443264A (en) * | 2014-12-02 | 2015-03-25 | 常熟市华阳机械制造厂 | Corrosion resistant marine wheel carrier |
| CN106086557B (en) * | 2016-06-08 | 2019-12-20 | 南昌大学 | Mn-Cu-Al thermosensitive damping alloy material and preparation method thereof |
| CN107012417B (en) * | 2017-06-06 | 2018-06-19 | 东北大学 | A kind of preparation method of high-intensity high-damping MnCu based alloys |
| CN108315616B (en) * | 2018-05-03 | 2019-06-07 | 西南交通大学 | A kind of polynary Mn-Cu base damping alloy and preparation method thereof |
Citations (3)
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| CN1049382A (en) * | 1989-08-10 | 1991-02-20 | 哈尔滨工业大学 | Alloy containing iron, manganese, silicon and nickel by form memory |
| JP2001279360A (en) * | 2000-03-30 | 2001-10-10 | Toshiba Corp | Mn SERIES ALLOY |
| 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 |
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2006
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Patent Citations (3)
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|---|---|---|---|---|
| CN1049382A (en) * | 1989-08-10 | 1991-02-20 | 哈尔滨工业大学 | Alloy containing iron, manganese, silicon and nickel by form memory |
| JP2001279360A (en) * | 2000-03-30 | 2001-10-10 | Toshiba Corp | Mn SERIES ALLOY |
| 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 |
Non-Patent Citations (2)
| Title |
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| 锰基高阻尼合金的研究进展. 邓华铭，陈树川.金属功能材料，第7卷第2期. 2004 |
| 锰基高阻尼合金的研究进展. 邓华铭，陈树川.金属功能材料，第7卷第2期. 2004 * |
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Assignee: Wuxi Kehong Nameplate Co., Ltd. Assignor: Jiangying Professional Technology College Contract record no.: 2011320000163 Denomination of invention: Manganese-based memory alloy with high-strength, plasticity and damping performances and production thereof Granted publication date: 20090902 License type: Exclusive License Open date: 20060816 Record date: 20110304 |
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Granted publication date: 20090902 Termination date: 20140310 |