CN105603336A - Zirconium-based amorphous alloy and preparation method thereof - Google Patents
Zirconium-based amorphous alloy and preparation method thereof Download PDFInfo
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- CN105603336A CN105603336A CN201610023492.5A CN201610023492A CN105603336A CN 105603336 A CN105603336 A CN 105603336A CN 201610023492 A CN201610023492 A CN 201610023492A CN 105603336 A CN105603336 A CN 105603336A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
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Abstract
The invention discloses zirconium-based amorphous alloy and a preparation method thereof. The preparation method includes the steps of firstly, mixing a certain amount of metal according to the composition requirement of the zirconium-based amorphous alloy to obtain mixed material, wherein the composition of the zirconium-based amorphous alloy is ZraCubAlcNidXe, a, b, c, d and e are atomic percentage, 40</=a</=65, 10</=b</=30, 5</=c</=15, 1</=d</=15, 0</=e</=10, and X is one or more of Nb, Pd, Ti, Co, Fe, Hf, Si and Ta; secondly, adding the mixed material obtained in the first step into a smelting furnace, and smelting for 5-30 minutes after vacuumizing the smelting furnace or under inert gas protection; thirdly, deslagging and purifying alloy obtained after the smelting in the second step, and then pouring into a die with the thermal conductivity being not smaller than 20W/mK to allow the alloy to be cooled fast so as to form the zirconium-based amorphous alloy. The preparation method has the advantages that the prepared zirconium-based amorphous alloy is low in cost and good in glass forming ability.
Description
[technical field]
The present invention relates to a kind of zirconium-base amorphous alloy and preparation method thereof.
[background technology]
Amorphous metal or alloy refer to when material is cooling rapidly from liquid (or gaseous state), because having little time crystallization in chamberTemperature or low temperature retain the state of aggregation of liquid atomic lack of alignment, and its atom is no longer long-range order, periodicity and ruleArrange, but locate a kind of long-range lack of alignment state. Compare with common crystalline state Metal and Alloy, amorphous metal with closeBecause its disordered structure does not exist crystal grain, crystal boundary, also there is not the lattice defect such as dislocation, slippage in gold, therefore has higherIntensity hardness, high-wearing feature, good magnetic performance and corrosion resistance etc., can be applied to high-grade electronic product,Sports goods, luxury goods, Aero-Space etc. The non-crystaline amorphous metal of existing excellent performance has generally all added rare earth element,And rare earth element is expensive resource, and reserves are limited, and this causes the cost of non-crystaline amorphous metal higher, has greatly limited amorphousThe commercial applications of alloy.
[summary of the invention]
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, propose a kind of zirconium-base amorphous closingGold and preparation method thereof, the cost of the zirconium-base amorphous alloy obtaining is lower, and has good glass forming ability.
Technical problem of the present invention is solved by following technical scheme:
A preparation method for zirconium-base amorphous alloy, comprises the following steps: 1) according to the composition of following zirconium-base amorphous alloyRequire a certain amount of metal to mix, obtain mixed material; Consisting of of described zirconium-base amorphous alloy:ZraCubAlcNidXe, wherein, a, b, c, d, e is atomic percent, 40≤a≤65; 10≤b≤30; 5≤c≤ 15; 1≤d≤15; 0 < e≤10; X is Nb, Pd, Ti, Co, Fe, Hf, Si, in Ta one or more;2) by step 1) mixed material that obtains adds in smelting furnace, smelting furnace is evacuated to vacuum and is less than 10-2Pa orPerson, under the inert gas shielding of gas purity >=99.9%, is heated to above the temperature of the fusing point of melting alloy to be formed,Melting 5～30min; 3) by step 2) after the alloy slagging-off that obtains of melting purifies, in cast into molds, mould is for leadingThe material that heating rate is more than or equal to 20W/mK makes, and makes the described zirconium-base amorphous alloy of the alloy rapid cooling formation of energy.
In preferred technical scheme,
Described step 3) in, in cast into molds after, whole mould is applied to vibration of ultrasonic wave processing, ultrasonic power is2×104～6×104W。
Described step 3) in, mould is that the material that thermal conductivity is greater than 30W/mK makes.
Described step 1) in, the consisting of of described zirconium-base amorphous alloy: Zr55Cu20Al10Ni8.5Ti6.5。
Described step 1) in, the consisting of of described zirconium-base amorphous alloy: Zr65Cu8Al15Ni7Nb5。
Described step 1) in, the consisting of of described zirconium-base amorphous alloy: Zr62Cu20Al7Ni7Pd4。
Described step 1) in, the consisting of of described zirconium-base amorphous alloy: Zr47Cu17Al15Ni12Ti9。
Technical problem of the present invention is solved by following further technical scheme:
A kind of zirconium-base amorphous alloy, makes according to preparation method as above.
The critical glass of described zirconium-base amorphous alloy forms and is of a size of 12mm～20mm.
The beneficial effect that the present invention is compared with the prior art is:
The preparation method of non-crystaline amorphous metal of the present invention, adopts zirconium matrix system, selects Cu, Al, Ni, X, X in componentSelect Nb, Pd, Ti, Co, Fe, Hf, Si, in Ta one or more, in conjunction with the technology controlling and process in melting and when casting,Finally make and meet the non-crystaline amorphous metal that component requires. In the non-crystaline amorphous metal obtaining, do not contain rare earth element, saved rareThe dependence of earth elements, and better through the forming of glass ability of experimental verification non-crystaline amorphous metal, critical glass forms size and can reachTo 12mm, maximum can reach 20mm, forms higher than the critical glass about the 6mm of existing zirconium-base amorphous alloySize. And, empirical tests, the zirconium-base amorphous alloy that the present invention makes also has excellent physicochemical property, as higher hardDegree, higher yield strength, good plasticity.
[detailed description of the invention]
Design of the present invention is: in existing non-crystaline amorphous metal, need to add rare earth element, reason is by adding rare earth unitThe methods such as element suppress alloy crystallization, amorphous alloy forming ability is strengthened, thereby had good glass forming ability.And the present invention is by the combination of component and technique, thus the prerequisite of not adding rare earth element in preparation processUnder, make the zirconium-base amorphous alloy making also there is good glass forming ability, its critical glass forms size maximum canReach 20mm.
The preparation method who proposes a kind of zirconium-base amorphous alloy in this detailed description of the invention, comprises the following steps:
1) according to the composition requirement of following zirconium-base amorphous alloy, a certain amount of metal is mixed, obtain mixed material;Consisting of of described zirconium-base amorphous alloy: ZraCubAlcNidXe, wherein, a, b, c, d, e is atomic percent,40≤a≤65; 10≤b≤30; 5≤c≤15; 1≤d≤15; 0 < e≤10; X is Nb, Pd, and Ti, Co, Fe,Hf, Si, in Ta one or more.
Element as above is as X element, and these element character are similar, and atomic radius and the performance of element differ notGreatly, all have and be suppressed to preferably nuclear capability, after combining according to a certain ratio with elements such as Zr, Cu, Al, Ni, canIn follow-up good inhibition alloy nucleation, form non-crystalline material, thereby needn't relying on the interpolation of rare earth element, realization reachesTo the object that suppresses alloy crystallization.
2) by step 1) mixed material that obtains adds in smelting furnace, smelting furnace is evacuated to vacuum and is less than 10-2PaOr under the inert gas shielding of gas purity >=99.9%, the fusing point that is heated to above melting alloy to be formed is (moltenPoint generally at 40～100 DEG C) temperature, melting 5～30min.
3) by step 2) after the alloy slagging-off that obtains of melting purifies, in cast into molds, mould is that thermal conductivity is greater thanThe material of 20W/mK makes, and makes the described zirconium-base amorphous alloy of the alloy rapid cooling formation of energy.
In above-mentioned steps, by melting by even mixed material melting, and by being smelted into after alloy, under system fusing pointFall, be down to 900 DEG C of left and right, be convenient to subsequent production. Casting cycle makes alloy be transformed into amorphous, when casting, and mould materialThe thermal conductivity of material is more than or equal to 20w/ (mK), is preferably greater than the material of 30w/ (mK), and thermal conductivity is higher, and alloy is quickCooling, thus alloy nucleation suppressed. Vacuum or inert gas shielding in fusion process, and in casting cycleThe thermal conductivity of mould all needs strict control, and thermal conductivity is larger, and material amorphous is more thorough; Vacuum is stricter, alloyGlass forming ability is stronger, thereby while cooperatively interacting, in conjunction with the improvement of component, finally in forming process, effectively suppressesAlloy nucleation, forms non-crystalline material, and obtains the good non-crystalline material of glass forming ability. Preferably, the material of mouldMatter is and the crystal structure of non-crystalline material and the large material of lattice constant difference that mould is selected with crystal structure and dot matrix normalThe large material of number difference, when alloy liquid contacts mould, the facilitation of die surface alloy Heterogeneous NucleationA little less than, can suppress preferably nucleation, promote to form non-crystalline material.
Further preferably, step 3) when casting, after the alloy slagging-off that melting is obtained is purified, in cast into molds after,Whole mould is added to the vibrations of ultrasonic wave high energy and process, make the rapid cooling formation zirconium-base amorphous alloy of alloy energy, be speciallyThe ingot bar of 12～20mm. Herein, the power 2 × 10 when the vibrations of ultrasonic wave high energy are processed4～6×104W. Super by addingAcoustic vibration processing, ultrasonic wave can further effectively suppress alloy heterogeneous nucleation process, promote non-crystalline material formation withAnd the growing up of crystal grain.
In this detailed description of the invention, by above-mentioned preparation method, do not rely on the interpolation of rare earth element, thereby make zirconium baseNon-crystaline amorphous metal, and can obtain relatively large body non-crystaline amorphous metal. The zirconium-base amorphous alloy making, with existing zirconium-base amorphous alloyCompare following advantage:
1) lower cost. The non-crystaline amorphous metal of existing excellent performance has much all added rare earth, and rare earth is expensive resource,And reserves are limited, greatly limit the commercial applications of non-crystaline amorphous metal. The above-mentioned metal adopting in this detailed description of the invention,Cost is all lower, can effectively accelerate amorphous industrialization.
2) good glass forming ability. The glass forming ability of non-crystaline amorphous metal is restriction amorphous commercial applications in enormous quantitiesThe biggest factor, after deliberation, added the methods such as rare earth element in the past and be mainly the effect that performance suppresses alloy nucleation, makeAmorphous alloy forming ability is strengthened. And the zirconium-base amorphous alloy making in this detailed description of the invention is not adding rare earth elementPrerequisite under, also have good glass forming ability, empirical tests, its critical glass forms and is of a size of 15mm～20mm.
3) excellent physicochemical property, as higher hardness, higher yield strength, excellent corrosion resistance, good plasticity.
The cost of the product making in this detailed description of the invention is lower, and has good glass forming ability, has simultaneouslyHigh strength, hardness, wearability, corrosion resistance, better plasticity, feature cheaply, be applicable to business application on a large scaleEmpirical tests.
As follows, the performance of the zirconium-base amorphous alloy material that checking makes by experiment.
Embodiment 1
1) according to Zr55Cu20Al10Ni8.5Ti6.5Composition mix a certain amount of metal, obtain mixed material.
2) mixed material is added in smelting furnace, smelting furnace is vacuumized, vacuum is less than 10-2Pa, is heated to 920DEG C, smelting time is 5-30min.
3) melting is obtained after alloy slagging-off purification, in cast into molds, the thermal conductivity of the material of mould is 35W/mK,Make the rapid cooling formation zirconium-base amorphous alloy of alloy energy.
Embodiment 2
1) according to Zr65Cu8Al15Ni7Nb5Composition mix a certain amount of metal, obtain mixed material.
2) mixed material is added in smelting furnace, smelting furnace is vacuumized, vacuum is less than 10-2Pa, is heated to 920DEG C, smelting time is 5-30min.
3) melting is obtained after alloy slagging-off purification, in cast into molds, the thermal conductivity of the material of mould is 35W/mK,Make the rapid cooling formation zirconium-base amorphous alloy of alloy energy.
Embodiment 3
1) according to Zr62Cu20Al7Ni7Pd4Composition mix a certain amount of metal, obtain mixed material.
2) mixed material is added in smelting furnace, smelting furnace is vacuumized, vacuum is less than 10-2Pa, is heated to 950DEG C, smelting time is 5-30min.
3) melting is obtained after alloy slagging-off purification, in cast into molds, the thermal conductivity of the material of mould is 35W/mK,Make the rapid cooling formation zirconium-base amorphous alloy of alloy energy.
Embodiment 4
1) according to Zr47Cu17Al15Ni12Ti9Composition mix a certain amount of metal, obtain mixed material.
2) mixed material is added in smelting furnace, smelting furnace is vacuumized, vacuum is less than 10-2Pa, is heated to 940DEG C, smelting time is 5-30min.
3) melting is obtained after alloy slagging-off purification, in cast into molds, the thermal conductivity of the material of mould is 35W/mK,Make the rapid cooling formation zirconium-base amorphous alloy of alloy energy.
Testing the ingot bar making in each embodiment, is also that the performance of zirconium-base amorphous alloy is as shown in the table:
From the data of upper table, the zirconium-base amorphous alloy that embodiment 1～4 makes does not rely on rare earth element, and obtainGlass forming ability is better, reaches 12～20mm, higher than the critical glass about the 6mm of existing zirconium-base amorphous alloyGlass forms size. Glass forming ability is better, thereby can expand commercial applications in enormous quantities. Meanwhile, strong according to surrenderThe test data of degree, fracture strength and plastic deformation is also known, and zirconium-base amorphous alloy also has excellent physicochemical property,Comprise hardness, higher yield strength, good plasticity.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assertSpecific embodiment of the invention is confined to these explanations. For general technical staff of the technical field of the invention,Make without departing from the inventive concept of the premise some substituting or obvious modification, and performance or purposes identical, all answerWhen being considered as belonging to protection scope of the present invention.
Claims (9)
1. a preparation method for zirconium-base amorphous alloy, is characterized in that: comprise the following steps: 1) according to following zirconium baseThe composition requirement of non-crystaline amorphous metal mixes a certain amount of metal, obtains mixed material; Described zirconium-base amorphous alloyConsist of: ZraCubAlcNidXe, wherein, a, b, c, d, e is atomic percent, 40≤a≤65; 10≤b≤30; 5≤c≤15; 1≤d≤15; 0 < e≤10; X is Nb, Pd, and Ti, Co, Fe, Hf, Si, a kind of in TaOr multiple; 2) by step 1) mixed material that obtains adds in smelting furnace, smelting furnace is evacuated to vacuum and is less than10-2Pa or under the inert gas shielding of gas purity >=99.9%, is heated to above the molten of melting alloy to be formedThe temperature of point, melting 5～30min; 3) by step 2) after the alloy slagging-off that obtains of melting purifies, in cast into molds,Mould is that the material that thermal conductivity is more than or equal to 20W/mK makes, and makes the alloy can described zirconium-base amorphous the closing of rapid cooling formationGold.
2. the preparation method of zirconium-base amorphous alloy according to claim 1, is characterized in that: described step 3) in,After in cast into molds, whole mould is applied to vibration of ultrasonic wave processing, ultrasonic power is 2 × 104～6×104W。
3. the preparation method of zirconium-base amorphous alloy according to claim 1, is characterized in that: described step 3) in,Mould is that the material that thermal conductivity is greater than 30W/mK makes.
4. the preparation method of zirconium-base amorphous alloy according to claim 1, is characterized in that: described step 1) in,Consisting of of described zirconium-base amorphous alloy: Zr55Cu20Al10Ni8.5Ti6.5。
5. the preparation method of zirconium-base amorphous alloy according to claim 1, is characterized in that: described step 1) in,Consisting of of described zirconium-base amorphous alloy: Zr65Cu8Al15Ni7Nb5。
6. the preparation method of zirconium-base amorphous alloy according to claim 1, is characterized in that: described step 1) in,Consisting of of described zirconium-base amorphous alloy: Zr62Cu20Al7Ni7Pd4。
7. the preparation method of zirconium-base amorphous alloy according to claim 1, is characterized in that: described step 1) in,Consisting of of described zirconium-base amorphous alloy: Zr47Cu17Al15Ni12Ti9。
8. a zirconium-base amorphous alloy, is characterized in that: according to the preparation method's system described in claim 1～7 any one.
9. zirconium-base amorphous alloy according to claim 8, is characterized in that: described zirconium-base amorphous alloy criticalGlass forms and is of a size of 12mm～20mm.
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Cited By (15)
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| CN108193147A (en) * | 2018-02-07 | 2018-06-22 | 瑞声精密制造科技(常州)有限公司 | A kind of zirconium-base amorphous alloy material of high tenacity and preparation method thereof |
| CN108220827A (en) * | 2018-01-02 | 2018-06-29 | 歌尔股份有限公司 | Zirconium-base amorphous alloy and preparation method thereof |
| CN108411225A (en) * | 2018-03-27 | 2018-08-17 | 深圳市锆安材料科技有限公司 | A kind of zirconium-base amorphous alloy and preparation method thereof |
| CN108707844A (en) * | 2018-05-22 | 2018-10-26 | 大连理工大学 | A kind of low cost Zr bast block metal glass and preparation method thereof |
| CN110331348A (en) * | 2019-05-30 | 2019-10-15 | 深圳大学 | Amorphous alloy material, amorphous alloy flexbile gear and preparation method thereof |
| CN111549302A (en) * | 2020-05-26 | 2020-08-18 | 南京工业大学 | Non-biotoxicity Zr-based amorphous alloy and preparation method thereof |
| CN112593123A (en) * | 2020-12-14 | 2021-04-02 | 昆明理工大学 | Zirconium-based amorphous particle reinforced aluminum-based composite material and preparation method thereof |
| CN113528986A (en) * | 2021-07-15 | 2021-10-22 | 深圳大学 | Ultrahigh-toughness large-size zirconium-based amorphous alloy and preparation method and application thereof |
| CN113619211A (en) * | 2021-07-08 | 2021-11-09 | 深圳大学 | Anti-twisting bearing tray in badminton shoe and production method thereof |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN114032478A (en) * | 2021-11-11 | 2022-02-11 | 盘星新型合金材料(常州)有限公司 | Zr-based amorphous alloy with plasticity and preparation method thereof |
| CN114214575A (en) * | 2021-12-18 | 2022-03-22 | 东莞宜安新材料研究院有限公司 | Zirconium-based amorphous alloy material and preparation method thereof |
| CN114381674A (en) * | 2021-12-24 | 2022-04-22 | 盘星新型合金材料(常州)有限公司 | ZrCu-based amorphous alloy powder and preparation method thereof |
| CN115478234A (en) * | 2022-09-16 | 2022-12-16 | 盘星新型合金材料(常州)有限公司 | Be-free zirconium-based amorphous alloy with plasticity and preparation method thereof |
| US20230070081A1 (en) * | 2021-08-17 | 2023-03-09 | City University Of Hong Kong | Metallic glass |
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| CN108220827A (en) * | 2018-01-02 | 2018-06-29 | 歌尔股份有限公司 | Zirconium-base amorphous alloy and preparation method thereof |
| CN108193147A (en) * | 2018-02-07 | 2018-06-22 | 瑞声精密制造科技(常州)有限公司 | A kind of zirconium-base amorphous alloy material of high tenacity and preparation method thereof |
| CN108411225A (en) * | 2018-03-27 | 2018-08-17 | 深圳市锆安材料科技有限公司 | A kind of zirconium-base amorphous alloy and preparation method thereof |
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| CN108707844A (en) * | 2018-05-22 | 2018-10-26 | 大连理工大学 | A kind of low cost Zr bast block metal glass and preparation method thereof |
| CN110331348A (en) * | 2019-05-30 | 2019-10-15 | 深圳大学 | Amorphous alloy material, amorphous alloy flexbile gear and preparation method thereof |
| CN111549302A (en) * | 2020-05-26 | 2020-08-18 | 南京工业大学 | Non-biotoxicity Zr-based amorphous alloy and preparation method thereof |
| CN112593123B (en) * | 2020-12-14 | 2021-11-09 | 昆明理工大学 | Zirconium-based amorphous particle reinforced aluminum-based composite material and preparation method thereof |
| CN112593123A (en) * | 2020-12-14 | 2021-04-02 | 昆明理工大学 | Zirconium-based amorphous particle reinforced aluminum-based composite material and preparation method thereof |
| CN113619211A (en) * | 2021-07-08 | 2021-11-09 | 深圳大学 | Anti-twisting bearing tray in badminton shoe and production method thereof |
| CN113528986A (en) * | 2021-07-15 | 2021-10-22 | 深圳大学 | Ultrahigh-toughness large-size zirconium-based amorphous alloy and preparation method and application thereof |
| US20230070081A1 (en) * | 2021-08-17 | 2023-03-09 | City University Of Hong Kong | Metallic glass |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
| CN114032478A (en) * | 2021-11-11 | 2022-02-11 | 盘星新型合金材料(常州)有限公司 | Zr-based amorphous alloy with plasticity and preparation method thereof |
| CN114214575A (en) * | 2021-12-18 | 2022-03-22 | 东莞宜安新材料研究院有限公司 | Zirconium-based amorphous alloy material and preparation method thereof |
| CN114381674A (en) * | 2021-12-24 | 2022-04-22 | 盘星新型合金材料(常州)有限公司 | ZrCu-based amorphous alloy powder and preparation method thereof |
| CN115478234A (en) * | 2022-09-16 | 2022-12-16 | 盘星新型合金材料(常州)有限公司 | Be-free zirconium-based amorphous alloy with plasticity and preparation method thereof |
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