CN101225486A - Copper-based in-situ composite material and preparation method thereof - Google Patents
Copper-based in-situ composite material and preparation method thereof Download PDFInfo
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- CN101225486A CN101225486A CNA2008100172943A CN200810017294A CN101225486A CN 101225486 A CN101225486 A CN 101225486A CN A2008100172943 A CNA2008100172943 A CN A2008100172943A CN 200810017294 A CN200810017294 A CN 200810017294A CN 101225486 A CN101225486 A CN 101225486A
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- 239000010949 copper Substances 0.000 description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 229910052802 copper Inorganic materials 0.000 description 35
- 230000001419 dependent effect Effects 0.000 description 24
- 239000002131 composite material Substances 0.000 description 23
- 239000011651 chromium Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 19
- 238000011065 in-situ storage Methods 0.000 description 19
- 239000011159 matrix material Substances 0.000 description 17
- 239000000956 alloy Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 11
- 238000010622 cold drawing Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 238000005266 casting Methods 0.000 description 9
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 8
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 8
- 230000006698 induction Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 241000555268 Dendroides Species 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention relates to a copper-based in-situ composite material and the preparation method, belonging to the copper-based alloy technical field; wherein the chromium accounts for 6 to 16% (weight percentage), the zirconium accounts for 0.02 to 0.2% and the rest is copper. The preparation technique comprising steps that: a quantity of chromium, zirconium and copper according to the weight percentage are mixed and melted into ingots; the ingots is taken for hot forging and solid solution; then for multi-pass cold drawing at ambient temperature and heat treatment in the process of cold drawing. The copper-based in-situ composite material prepared by the preparation method has the advantages of tensile strength of 850 to 1300MPa, conductivity of 70 to 80%IACS and softening temperature of 500 to 550 centigrade; thereby can be widely used for long pulse strong magnetic field coil conductor materials, contact line and integrated circuit lead frame materials of trolleys and electric locomotives.
Description
Technical field
The present invention relates to the copper-based alloy material technical field, particularly a kind of copper-based in-situ composite material and preparation technology thereof.
Background technology
High strength and high conductivity are a pair of conflicting characteristic, and be no exception to Cu alloy material.In the Cu alloy material research field, mainly solve the contradiction of its high strength and high conductivity by alloying and matrix material method.At present, the multi-element composite micro-alloying technology more and more comes into one's own, and has become the further effective means of improving copper alloy intensity and conductivity.
Copper-based in-situ is compound to be meant in copper and to add the alloying element that down mutually do not dissolve or have minimum solid solubility solid-state with it, makes the two-phase complex body, its under as cast condition by the copper matrix be dendroid or second phase composite of particulate state existence.Through after the violent cold deformation, second changes the fiber that draws on the direction mutually into along the line, and the copper matrix is keeping high electroconductibility as a result, and its fiber is keeping high intensity, thereby obtains fibre-reinforced matrix material.
Cu and some magnesium-yttrium-transition metals can obtain the good combination of intensity and electroconductibility as formation alloys (being no more than 20% the magnesium-yttrium-transition metal volume content) such as Nb, Ag, Fe, Cr, Mo, V and W after deformation.Its basic reason is that Cu and these magnesium-yttrium-transition metals do not dissolve or have only minimum solid solubility mutually at solid-state time, the alloy that Cu and magnesium-yttrium-transition metal form, be by pure Cu phase and pure magnesium-yttrium-transition metal phase composite basically under as cast condition, and magnesium-yttrium-transition metal is embedded in the Cu matrix with dendroid or particulate state, after deformation, magnesium-yttrium-transition metal has formed mutually and has been parallel to the fiber that line draws direction, and the fiber in the alloy has high strength like this, and the copper matrix has also kept good electrical conductivity simultaneously.
The high strength of copper-based in-situ composite material is mainly derived from substructure (dislocation, subgrain boundary, crystal boundary, precipitated phase) and strengthens and fiber strengthening, the extraordinary high strength that it had is difficult to make an explanation by the mixing rule of routine, find the in-situ composite of the high-strength highly-conductive of Cu-(10～30) Nb from initial 1978 Beck, people have carried out research extensively and profoundly to its strengthening mechanism for this reason.When considering each volume fraction mutually, consider the effect of phase interface as Raabe and Hangen etc. again, the line yield strength of drawing the Cu-Nb matrix material of having utilized the mixing rule analog calculation revised, its result and experimental value are better identical; Moreover hinder dislocation motion based on crystal boundary, cause piling up of dislocations and stress concentration and the obstacle model of the dislocations strengthening that proposes by Funkenbusch; And strengthen the phase interface that proposes by Verhoeven based on the cold deformation perlite and strengthen model etc.According to existing numerous results of study, interface enhancing and the coefficient result of dislocations strengthening when the high-intensity reason far above mixing rule that copper-based in-situ composite material has may be the two-phase compatible deformation.
Though Cu-Ag, Cu-Nb original position deformed composite material can reach the coupling of superstrength and good electrical conductivity,, and influenced its application prospect because Ag and Nb are precious metals.Cu-Cr, Cu-Fe etc. are present main research focuses because the prices of raw and semifnished materials are lower.But solid-state Fe down and Cu have certain solid solubility, influence its conductivity, and the intensity of Cu-Cr are on the low side.
Summary of the invention
The object of the present invention is to provide a kind of copper-based in-situ composite material that improved intensity and conductivity are taken into account on copper base binary alloy (Cu-Cr) basis.Another step purpose of the present invention provides a kind of preparation method of above-mentioned copper-based in-situ composite material, this method can be when improving composite material strength, can improve separating out of Cr, improve the anti-softening temperature of this matrix material, reduce the influence of trace alloying element its electric conductivity.
In order to realize above-mentioned technical purpose, technical scheme of the present invention is achieved in that
A kind of copper-based in-situ composite material is characterized in that, contains weight percent and be 6～16% chromium, 0.02～0.2% zirconium, all the other are copper.
The further optimum ratio of this technical scheme is that to contain weight percent be 9～15% chromium, 0.06～0.1% zirconium, and all the other are copper.
The best optimum ratio of this technical scheme is that to contain weight percent be 12% chromium, 0.08% zirconium, and all the other are copper.
Another technical scheme of the present invention: a kind of preparation method of copper-based in-situ composite material mainly comprises the steps:
(1) take by weighing chromium, zirconium, copper respectively according to above-mentioned weight percent, mixed smelting, founding becomes Cu-Cr-Zr ternary alloy ingot casting;
(2) ingot casting is carried out forge hot under 900～980 ℃, carry out solution treatment then, solid solubility temperature is 950～1000 ℃, and solution time is 1～2h, obtains the solution treatment material;
(3) at room temperature material after the solution treatment is carried out the multi-pass cold drawing, final drawing dependent variable η is 6～7, carries out intermediate heat treatment in multi-pass cold drawing process.
Preparation method's of the present invention further optimization is that described intermediate heat treatment is twice, when cold drawing dependent variable η is between 3.5～4.1, carries out the intermediate heat treatment first time, 550～450 ℃ of temperature, time 1h; When cold drawing dependent variable η is between 4.5～5.1, carry out the intermediate heat treatment second time, 500～400 ℃ of temperature, time 1h.
According to the copper-based in-situ composite material that above-mentioned preparation method obtains, its tensile strength is 850～1300MPa, and specific conductivity is 70～80%IACS, and softening temperature is 500～550 ℃.
Because copper-based in-situ composite material of the present invention by introduce the alloy element Zr of trace in the Cu-Cr binary alloy, has improved the answer and the recrystallization temperature of Cu matrix under the high temperature, and can promote that Cr separates out under the low temperature from Cu.Among the present invention, the introducing of Zr has considered mainly that also it has significant ageing strengthening, the too high electroconductibility that will reduce alloy greatly of content, and that content is crossed low its strengthening effect that is had is not remarkable, therefore, through test in a large number, wherein Zr content is 0.02～0.20% more suitable.
Preparation method's of the present invention key character is to have adopted intermediate heat treatment, and this technological process makes Cr fully separate out from matrix with the nano level dispersed granules; Simultaneously nanofiber enhancing and nanoparticle dispersion-strengthened are combined, when significantly improving the strength of materials, improve its conductivity and high temperature softening resistance energy, its tensile strength can reach 850～1300MPa, electric conductivity reaches 70～80%IACS, softening temperature reaches 500～550 ℃, can satisfy the performance requirement of the field such as osculatory, circuit lead frame material of the high-strength magneticfield coil conductor material of long pulse, electric car and electric locomotive to high-intensity high-conductivity copper alloy.
Embodiment
Embodiment 1: with weight ratio be 6% pure chromium, 0.03% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 900 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 950 ℃, and solution time is 1h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.6 o'clock, 450 ℃ of intermediate heat treatment of carrying out soaking time 1h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 4.8 o'clock, 400 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.7, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 900MPa, electric conductivity 76%IACS, 520 ℃ of softening temperatures.
Embodiment 2: with weight ratio be 6% pure chromium, 0.15% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 900 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 950 ℃, and solution time is 1h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.9 o'clock, 450 ℃ of intermediate heat treatment of carrying out soaking time 1h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 5.1 o'clock, 400 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.2, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 850MPa, electric conductivity 75%IACS, 500 ℃ of softening temperatures.
Embodiment 3: with weight ratio be 9% pure chromium, 0.03% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 900 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 960 ℃, and solution time is 1.5h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.8 o'clock, 500 ℃ of intermediate heat treatment of carrying out soaking time 1h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 4.6 o'clock, 450 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.9, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 1087MPa, electric conductivity 79%IACS, 500 ℃ of softening temperatures.
Embodiment 4: with weight ratio be 12% pure chromium, 0.08% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 930 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 980 ℃, and solution time is 1.5h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.9 o'clock, 500 ℃ of intermediate heat treatment of carrying out soaking time 1h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 4.6 o'clock, 500 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.7, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 1195MPa, electric conductivity 77%IACS, 540 ℃ of softening temperatures.
Embodiment 5: with weight ratio be 12% pure chromium, 0.15% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 930 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 980 ℃, and solution time is 1.5h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.9 o'clock, 500 ℃ of intermediate heat treatment of carrying out soaking time 1h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 4.6 o'clock, 500 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.7, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 1130MPa, electric conductivity 75%IACS, 540 ℃ of softening temperatures.
Embodiment 6: with weight ratio be 9% pure chromium, 0.10% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 900 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 960 ℃, and solution time is 1h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.7 o'clock, 500 ℃ of intermediate heat treatment of carrying out soaking time 1 h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 4.8 o'clock, 450 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.5, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 1120MPa, electric conductivity 78%IACS, 500 ℃ of softening temperatures.
Embodiment 7: with weight ratio be 15% pure chromium, 0.06% zirconium sponge, all the other are electrolytic copper melting in the induction furnace frequently in a vacuum, founding becomes the alloy cast ingot of Φ 82mm, at 940 ℃ ingot casting is carried out forge hot and becomes the bar of diameter about Φ 23mm.Solution treatment after the forge hot is carried out under nitrogen protection, and its solid solubility temperature is 1000 ℃, and solution time is 2h, the back shrend of coming out of the stove.Carry out the cold drawing of multi-pass subsequently, being drawn to dependent variable η is 3.9 o'clock, 500 ℃ of intermediate heat treatment of carrying out soaking time 1h; Then carry out the multi-pass drawing again, being drawn to dependent variable η is 4.6 o'clock, 450 ℃ of intermediate heat treatment of carrying out 1h, Cr is fully separated out from matrix; Again it is carried out the multi-pass drawing at last, to dependent variable η be 6.7, thereby prepare copper-based in-situ composite material of the present invention (Cu-Cr-Zr), its tensile strength 1260MPa, electric conductivity 76%IACS, 500 ℃ of softening temperatures.
Claims (6)
1. a copper-based in-situ composite material is characterized in that, contains weight percent and be 6～16% chromium, 0.02～0.2% zirconium, all the other are copper.
2. according to claims 1 described a kind of copper-based in-situ composite material, it is characterized in that containing weight percent is 9～15% chromium, 0.06～0.1% zirconium, all the other are copper.
3. according to claims 2 described a kind of copper-based in-situ composite materials, it is characterized in that containing weight percent is 12% chromium, 0.08% zirconium, all the other are copper.
4. according to the preparation method of the arbitrary described copper-based in-situ composite material of claim 1～3, it is characterized in that, comprise the steps:
(1) take by weighing chromium, zirconium, copper respectively according to above-mentioned weight percent, mixed smelting, founding becomes Cu-Cr-Zr ternary alloy ingot casting;
(2) ingot casting is carried out forge hot under 900～950 ℃, carry out solution treatment then, solid solubility temperature is 950～1000 ℃, and solution time is 1～2h, obtains the solution treatment material;
(3) at room temperature material after the solution treatment is carried out the multi-pass cold drawing, final drawing dependent variable η is 6～7, carries out intermediate heat treatment in multi-pass cold drawing process.
5. according to the preparation method of the described copper-based in-situ composite material of claim 4, it is characterized in that described intermediate heat treatment is twice, when cold drawing dependent variable η is between 3.5～4.1, carry out the intermediate heat treatment first time, 550～450 ℃ of temperature, time 1h; When cold drawing dependent variable η is between 4.5～5.1, carry out the intermediate heat treatment second time, 500～400 ℃ of temperature, time 1h.
6. according to the copper-based in-situ composite material of preparation method's gained of the described copper-based in-situ composite material of claim 5, it is characterized in that tensile strength is 850～1300MPa, specific conductivity is 70～80%IACS, and softening temperature is 500～550 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531149B (en) * | 2009-04-09 | 2011-04-20 | 中铁电气化局集团有限公司 | Preparation method of overlength Cu-Cr-Zr alloyed contact line |
| CN102921940A (en) * | 2012-09-20 | 2013-02-13 | 中国石油大学(北京) | Iron nano belt and preparation method thereof |
| CN103456385A (en) * | 2013-09-04 | 2013-12-18 | 江西理工大学 | High-strength and high-conductivity Cu-Cr-Ti alloy conductor and manufacturing method thereof |
| CN108611520A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN110438366A (en) * | 2019-08-06 | 2019-11-12 | 西安西电光电缆有限责任公司 | High-strength highly-conductive precipitation strength chromiumcopper conducting rod and its preparation method and application |
| CN113528883A (en) * | 2021-07-13 | 2021-10-22 | 上海理工大学 | Copper-niobium alloy for medical biopsy puncture needle |
| CN113528882A (en) * | 2021-07-13 | 2021-10-22 | 上海锐力医疗器械有限公司 | Application of copper-chromium alloy in biopsy puncture needle |
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2008
- 2008-01-15 CN CNA2008100172943A patent/CN101225486A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101531149B (en) * | 2009-04-09 | 2011-04-20 | 中铁电气化局集团有限公司 | Preparation method of overlength Cu-Cr-Zr alloyed contact line |
| CN102921940A (en) * | 2012-09-20 | 2013-02-13 | 中国石油大学(北京) | Iron nano belt and preparation method thereof |
| CN102921940B (en) * | 2012-09-20 | 2015-01-21 | 中国石油大学(北京) | Iron nano belt and preparation method thereof |
| CN103456385A (en) * | 2013-09-04 | 2013-12-18 | 江西理工大学 | High-strength and high-conductivity Cu-Cr-Ti alloy conductor and manufacturing method thereof |
| CN103456385B (en) * | 2013-09-04 | 2016-01-20 | 江西理工大学 | A kind of high-strength highly-conductive Cu-Cr-Ti alloy lead wire and preparation method thereof |
| CN108611520A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN108611520B (en) * | 2018-05-08 | 2019-05-31 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN110438366A (en) * | 2019-08-06 | 2019-11-12 | 西安西电光电缆有限责任公司 | High-strength highly-conductive precipitation strength chromiumcopper conducting rod and its preparation method and application |
| CN113528883A (en) * | 2021-07-13 | 2021-10-22 | 上海理工大学 | Copper-niobium alloy for medical biopsy puncture needle |
| CN113528882A (en) * | 2021-07-13 | 2021-10-22 | 上海锐力医疗器械有限公司 | Application of copper-chromium alloy in biopsy puncture needle |
| US11661643B2 (en) | 2021-07-13 | 2023-05-30 | Shanghai Ruizhikang Medical Technology Co., Ltd. | Use of copper-chromium alloy in biopsy puncture needle |
| US11959160B2 (en) | 2021-07-13 | 2024-04-16 | University Of Shanghai For Science And Technology | Copper-niobium alloy for medical biopsy puncture needle |
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