CN109355602A - With high glass forming ability without nickel without beryllium zirconium-base amorphous alloy and preparation and application - Google Patents

With high glass forming ability without nickel without beryllium zirconium-base amorphous alloy and preparation and application Download PDF

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CN109355602A
CN109355602A CN201811360924.7A CN201811360924A CN109355602A CN 109355602 A CN109355602 A CN 109355602A CN 201811360924 A CN201811360924 A CN 201811360924A CN 109355602 A CN109355602 A CN 109355602A
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nickel
amorphous alloy
zirconium
alloy
beryllium
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CN109355602B (en
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吕昭平
刘广来
吴渊
王辉
刘雄军
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • 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 belongs to block amorphous alloys, more particularly to have high glass forming ability without nickel without beryllium zirconium-base amorphous alloy and preparation and application, atomic percent expression formula of the no nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b≤27,5≤c≤9,2≤d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.The zirconium-based bulk amorphous alloy of the invention plastic deformation ability that preferentially ingredient has > 7% and yield strength more than 1600MPa, higher glass transformation temperature and initial crystallization temperature, wider supercooling liquid phase region, simultaneously without the biological incompatible element such as Ni, Be, have broad application prospects in fields such as sports equipment, medical instrument, high-end micromechanics components.

Description

With high glass forming ability without nickel without beryllium zirconium-base amorphous alloy and preparation and application
Technical field
The invention belongs to block amorphous alloys, and in particular to a kind of without metallic element Ni and Be to there is high glass to be formed Ability is without nickel without beryllium zirconium-base amorphous alloy and preparation and application.
Technical background
Amorphous alloy is a kind of alloy of the shortrange order longrange disorder obtained by melt supercooled, so that they have The incomparable functional characteristic of usual crystalline metallic material, for example high intensity, big elastic limit, high breaking strength, height are firmly It is degree, corrosion-resistant etc., structural material, Miniature precision device, in terms of have broad application prospects.
Since late nineteen nineties in last century, scientific research personnel is in succession in Pd base, La base, Mg base, Fe base, Ni all over the world All many body systems such as base, Zr base, rare-earth base obtain bulk amorphous materials.Zr is base block amorphous because it is with excellent non-among these Brilliant Forming ability and outstanding mechanical property and be concerned, especially in bio-medical material such as joint prosthesis, femoral head branch Biocompatibility that support body etc. has by it and compared to the low elasticity for having closer natural bone for medical stainless steel material Modulus and elastic limit and favored.Furthermore zirconium-base amorphous to possess better mechanical property such as height compared to other system amorphous Whiles intensity, high rigidity, wear resistant corrosion resistant, resistance to oxidation etc., it is also equipped with relatively lower material cost, this makes zirconium-base amorphous Alloy has bigger application prospect in fields such as engineering material, aerospace, sports equipments.However having for developing at present is strong The zirconium-base amorphous alloy of glass forming ability nearly all contains metallic nickel or beryllium.Nickel and beryllium be all a little high cell toxicity biologies not Compatible element rejects Be and Ni element, often pole especially in the amorphous alloy component of these high glass forming abilities The amorphous formation ability of the system is reduced greatly, and can not prepare large scale amorphous alloy.On the other hand these Zr bases containing Be Amorphous alloy brittleness at room temperature will lead to material and its practical application of unexpected catastrophic fracture limit occur.
Summary of the invention
The present invention develop it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, it is therefore intended that not only Be the and Ni element that there is toxic side effect to cell is removed, and there is strong glass forming ability, passes through conventional electric arc melting copper Mould suction casting method can prepare Centimeter Level block amorphous alloy, and the biocompatibility with larger temperature-room type plasticity deformability Amorphous alloy.
The technical scheme is that it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, it is described Atomic percent expression formula without nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b ≤ 27,5≤c≤9,2≤d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.
Further, it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, the no nickel is without beryllium zirconium base The atomic percent expression formula of amorphous alloy component are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b≤27,5≤c≤ 9,3≤d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.
Further, when M is Nb element, a=56, b=26.7, c=7.5, d=6.8, e=3, the no nickel is without the zirconium-base amorphous conjunction of beryllium The atomic percent expression formula of golden ingredient are as follows: Zr56Cu26.7Al7.5Co6.8Nb3, alloy is capable of forming large block amorphous critical dimension Not less than 10mm, plastic deformation is not less than 5%.
Further, M is Si element, and a=58, b=23, c=9, d=9, e=1, the no nickel is without beryllium zirconium-base amorphous alloy ingredient Atomic percent expression formula are as follows: Zr58Cu23Al9Co9Si1, alloy is capable of forming large block amorphous critical dimension not less than 10mm.
Further, M is Y element, a=57.3, b=25.7, c=6, d=9, e=2, the no nickel without beryllium zirconium-base amorphous alloy at The Zr divided57.3Cu25.7Al6Co9Y2, it is 10mm that alloy, which is capable of forming large block amorphous critical dimension, and plastic deformation is not less than 4%.
It is a further object of the present invention to provide above-mentioned no nickel without beryllium zirconium-base amorphous alloy using electric arc melting copper mold Method preparation, the specific steps are as follows:
1) quality being converted into according to the atomic ratio of expression formula cut respectively metal Zr, Cu of high-purity, Al, Co, Ag, Hf, Nb, Ge, Si, each element purity in 99.0wt% or more, removes the oxide skin on raw metal surface, and is surpassed using dehydrated alcohol Sound wave cleaning, and weighed by respective required quality.
2) step 1 treated raw material is deposited in non-consumable arc furnace water jacketed copper crucible by fusing point sequence In, fire door is then shut off to furnace chamber pumping high vacuum to 3*10-3Pa is hereinafter, be then passed through argon gas, and carry out oxygen consumption with pure titanium, then Melt back raw material at least 5 times, obtain the uniform master alloy ingot of melting；
3) melted ingot casting is inhaled using copper mold casting and casts cylindrical non-crystalline material.
A kind of zirconium-based bulk amorphous material that above-mentioned preparation method obtains is applied to sports equipment, medical instrument, high-end micro- Component of machine preparation technical field.
The beneficial effects of the present invention are:
1) alloy system is free of Be, Ni element harmful to organism, and biocompatibility is excellent.
2) alloy system has very strong glass forming ability, and the preferentially ingredient prepared by the method for copper mold is non- Peritectic alloy critical dimension is not less than 10mm, can satisfy the size requirement of amorphous alloy manufacture field.
3) alloy has preferable temperature-room type plasticity deformability, and plastic strain is greater than 7% when preferentially ingredient is broken.
Zr prepared by Fig. 1 embodiment of the present invention 1,2 and 357Cu26.7Al7.5Co5.8Hf3、Zr57Cu26.7Al7.5Co5.8Nb3, it is big Block amorphous alloy diameter 10mm sample and Zr57Cu26.7Al7.5Co5.8Ag3The XRD diagram of 5mm sample.
Zr prepared by Fig. 2 embodiment of the present invention 157Cu26.7Al7.5Co5.8Hf3Bulk amorphous alloys DSC curve (heating rate 20K/min) schematic diagram.
Zr prepared by Fig. 3 embodiment of the present invention 157Cu26.7Al7.5Co5.8Hf3The compression stress of bulk amorphous alloys strains bent Line schematic diagram.
Zr prepared by Fig. 4 embodiment of the present invention 257Cu26.7Al7.5Co5.8Nb3Bulk amorphous alloys DSC curve (heating rate 20K/min) schematic diagram.
Zr prepared by Fig. 5 embodiment of the present invention 257Cu26.7Al7.5Co5.8Nb3The compression stress of bulk amorphous alloys strains bent Line schematic diagram.
Zr prepared by Fig. 6 embodiment of the present invention 257Cu26.7Al7.5Co5.8Ag3Bulk amorphous alloys DSC curve (heating rate 20K/min) schematic diagram.
Specific embodiment
Technical scheme is described further combined with specific embodiments below.
The present invention it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, the no nickel is non-without beryllium zirconium base The atomic percent expression formula of peritectic alloy ingredient are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b≤27,5≤c≤9,2 ≤ d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.
The present invention it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, which is characterized in that the nothing Atomic percent expression formula of the nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b≤ 27,5≤c≤9,3≤d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.
A method of above-mentioned no nickel is prepared without beryllium zirconium-base amorphous alloy using electric arc melting copper mold, specific steps It is as follows:
Step 1: design ingredient, the quality being converted into according to the atomic ratio of expression formula cut respectively high-purity metal Zr, Cu, Al, Co, Ag, Hf, Nb, Ge, Si, each element purity in 99.0wt% or more, removes the oxide skin on raw metal surface, and makes Ultrasonic cleaning is carried out with dehydrated alcohol, and is weighed by respective required quality；
Step 2: step 1 treated raw material is deposited in non-consumable arc furnace water jacketed copper crucible by fusing point sequence In, fire door is then shut off to furnace chamber pumping high vacuum to 3*10-3Pa is hereinafter, be then passed through argon gas, and carry out oxygen consumption with pure titanium, then Melt back raw material at least 5 times, obtain the uniform master alloy ingot of melting；
Step 3: melted ingot casting inhaled using copper mold casting cast it is cylindrical without nickel without beryllium zirconium-base amorphous alloy material Material.
Critical dimension of no nickel without beryllium zirconium-base amorphous alloy is prepared not less than 10mm, plastic deformation ability in the method Not less than 7%.
A kind of zirconium-based bulk amorphous material that above-mentioned preparation method obtains is applied to sports equipment, medical instrument, high-end micro- Component of machine preparation technical field.
Embodiment 1:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 57%, Cu 26.7%, Al7.5%, Co5.8%, Hf3% The Zr of formation57Cu26.7Al7.5Co5.8Hf3With strong glass forming ability, can get under conditions of electric arc melting copper mold Critical dimension is not less than the block amorphous alloy of 10mm.
As shown in fig. 1, Zr57Cu26.7Al7.5Co5.8Hf3The XRD spectrum of 10mm sample only has typical amorphous diffusing scattering Peak illustrates that the alloy of 10mm is amorphous phase, which has strong amorphous formation ability.
Fig. 2 show Zr57Cu26.7Al7.5Co5.8Hf3The DSC curve of sample, heating rate are 20K/min, can from figure To find out glass transformation temperature (Tg), initial crystallization temperature (Tx) and supercooled liquid phase sector width (Tx-Tg) it is respectively 653K, 730K And 77K.
The room temperature compression stress strain curve of the amorphous alloy as shown in Figure 3,1.0*10-4s-1.As can be seen that alloy exists Reaching yield strength, there is no the catastrophic fractures of generation immediately later, but by one section of plastic deformation (> 6%), show the amorphous Alloy has good plastic deformation ability.
Embodiment 2:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 57%, Cu 26.7%, Al7.5%, Co5.8%, Nb 3% Zr formed57Cu26.7Al7.5Co5.8Nb3With strong amorphous formation ability, can be obtained under conditions of electric arc melting copper mold Obtain the block amorphous alloy that critical dimension is up to 10mm.
As shown in fig. 1, Zr57Cu26.7Al7.5Co5.8Nb3The XRD spectrum of 10mm sample has typical amorphous diffusing scattering peak, Certainly occurs a small spike at the first scattering peak, this illustrates that the alloy overwhelming majority of 10mm is all amorphous phase, the conjunction Gold still has stronger glass forming ability.
Fig. 4 show Zr57Cu26.7Al7.5Co5.8Nb3The DSC curve of sample, heating rate are 20K/min, can from figure To find out glass transformation temperature (Tg), initial crystallization temperature (Tx) and supercooled liquid phase sector width (Tx-Tg) it is respectively 668K, 747K And 79K.
The room temperature compression stress strain curve of the amorphous alloy as shown in Figure 5, strain rate 1.0*10-4s-1.It can see Out, there is no the catastrophic fractures of generation immediately after reaching yield strength for alloy, but pass through one section of plastic deformation (> 7%), Show that the amorphous alloy has good plastic deformation ability.
Embodiment 3:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 57%, Cu 26.7%, Al7.5%, Co5.8%, Ag3% The Zr of formation57Cu26.7Al7.5Co5.8Ag3With strong amorphous formation ability, can get under conditions of electric arc melting copper mold Critical dimension is not less than the block amorphous alloy of 5mm.
As shown in fig. 1, Zr57Cu26.7Al7.5Co5.8Ag3The XRD spectrum of 5mm sample only has typical amorphous diffusing scattering Peak illustrates that the alloy of 5mm is amorphous phase, which has stronger glass forming ability.
Fig. 6 show Zr57Cu26.7Al7.5Co5.8Ag3The DSC curve of sample, heating rate are 20K/min, can from figure To find out glass transformation temperature (Tg), initial crystallization temperature (Tx) and supercooled liquid phase sector width (Tx-Tg) it is respectively 653K, 720K And 67K.
Embodiment 4:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 56%, Cu 26.7%, Al7.5%, Co6.8%, Hf 3% Zr formed56Cu26.7Al7.5Co6.8Hf3With strong glass forming ability, can be obtained under conditions of electric arc melting copper mold Obtain the block amorphous alloy that critical dimension is not less than 10mm.
Embodiment 5:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 56%, Cu 26.7%, Al 7.5%, Co6.8%, Y 3% Zr formed56Cu26.7Al7.5Co6.8Y3With strong glass forming ability, can be obtained under conditions of electric arc melting copper mold Obtain the block amorphous alloy that critical dimension is not less than 10mm.
Embodiment 6:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 58%, Cu 23%, Al 9%, Co9%, Si1% is formed Zr58Cu23Al9Co9Si1With strong glass forming ability, critical dimension can get under conditions of electric arc melting copper mold Block amorphous alloy not less than 10mm.
Embodiment 7:
The atomic percent of each ingredient in zirconium-based bulk amorphous alloy are as follows: Zr 58%, Cu 27%, Al 9%, Co3%, Ge3% is formed Zr58Cu27Al9Co3Ge3With strong glass forming ability, critical dimension can get under conditions of electric arc melting copper mold Block amorphous alloy not less than 10mm.
The beneficial effects of the present invention are:
4) alloy system is free of Be, Ni element harmful to organism, and biocompatibility is excellent.
5) alloy system has very strong glass forming ability, and the preferentially ingredient prepared by the method for copper mold is non- Peritectic alloy critical dimension is not less than 10mm, can satisfy the size requirement of amorphous alloy manufacture field.
6) alloy has preferable temperature-room type plasticity deformability, and plastic strain is greater than 7% when preferentially ingredient is broken.
Most highly preferred embodiment of the invention is described in detail above, but is not meant to the scope of the present invention Limitation, content is only the preferred embodiment of the present invention, should not be considered as limiting the scope of the invention.Fan Yiben All the changes and improvements made by patent application range etc., should still be within the scope of the patent of the present invention.

Claims (10)

1. it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, which is characterized in that the no nickel is without beryllium zirconium The atomic percent expression formula of base noncrystal alloy ingredient are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b≤27,5≤c ≤ 9,2≤d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.
2. it is a kind of with high glass forming ability without nickel without beryllium zirconium-base amorphous alloy, which is characterized in that the no nickel is without beryllium zirconium The atomic percent expression formula of base noncrystal alloy ingredient are as follows: ZraCubAlcCodMe, wherein 56≤a≤58,23≤b≤27,5≤c ≤ 9,3≤d≤9,1≤e≤3, M Nb, Hf, Ag, Y, Si or Ge, and a+b+c+d+e=100 need to be met.
3. no nickel according to claim 1 or 2 is without beryllium zirconium-base amorphous alloy, which is characterized in that when M be Nb element, a=56, B=26.7, c=7.5, d=6.8, e=3, atomic percent expression formula of the no nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: Zr56Cu26.7Al7.5Co6.8Nb3, alloy is capable of forming large block amorphous critical dimension not less than 10mm, and plastic deformation is not less than 5%。
4. no nickel according to claim 1 or 2 is without beryllium zirconium-base amorphous alloy, which is characterized in that M be Si element, a=58, b= 23, c=9, d=9, e=1, atomic percent expression formula of the no nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: Zr58Cu23Al9Co9Si1, alloy is capable of forming large block amorphous critical dimension not less than 10mm.
5. no nickel according to claim 1 or 2 is without beryllium zirconium-base amorphous alloy, which is characterized in that M is Y element, a=57.3, b =25.7, c=6, d=9, e=2, atomic percent expression formula of the no nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: Zr57.3Cu25.7Al6Co9Y2, it is 10mm that alloy, which is capable of forming large block amorphous critical dimension, and plastic deformation is not less than 4%.
6. no nickel according to claim 1 or 2 is without beryllium zirconium-base amorphous alloy, which is characterized in that M be Ag element, a=58, b= 27, c=9, d=3, e=3, atomic percent expression formula of the no nickel without beryllium zirconium-base amorphous alloy ingredient are as follows: Zr58Cu27Al9Co3Ag3, it is 10mm that alloy, which is capable of forming large block amorphous critical dimension to be not less than,.
7. no nickel according to claim 1 is without beryllium zirconium-base amorphous alloy, which is characterized in that when M is Si, a=58%, b=23%, Atomic percent expression formula of the no nickel without beryllium zirconium-base amorphous alloy ingredient that c=9%, d=9%, e=1% are formed are as follows: Zr58Cu23Al9Co9Si1Critical dimension is not less than the block amorphous alloy of 10mm.
8. a kind of have the zirconium-base amorphous without beryllium without nickel of high glass forming ability using the method preparation of electric arc melting copper mold The method of alloy, which is characterized in that specific step is as follows:
Step 1) cut respectively according to the quality that is converted into of atomic ratio of the expression formula of design ingredient high-purity metal Zr, Cu, Al, Co, Ag, Hf, Nb, Ge, Si, each element purity in 99.0wt% or more, removes the oxide skin on raw metal surface, and makes Ultrasonic cleaning is carried out with dehydrated alcohol, it is spare；
Step 1 treated raw material is deposited in non-consumable arc furnace water jacketed copper crucible by fusing point sequence by step 2 In, fire door is then shut off to furnace chamber pumping high vacuum to 3*10-3Pa is hereinafter, be then passed through argon gas, and carry out oxygen consumption with pure titanium, then Melt back raw material at least 5 times, obtain the uniform master alloy ingot of melting；
Step 3) melted ingot casting is inhaled using copper mold casting cast it is cylindrical without nickel without beryllium zirconium-base amorphous alloy.
9. according to the method described in claim 8, it is characterized in that, no nickel is prepared without beryllium zirconium-base amorphous alloy in the method Critical dimension be not less than 10mm, plastic deformation ability be not less than 7%.
10. a kind of preparation method as claimed in claim 8 obtain without nickel without beryllium zirconium-base amorphous alloy be applied to sports equipment, Medical instrument, high-end micromechanics components preparation technical field.
CN201811360924.7A 2018-11-15 2018-11-15 Nickel-free beryllium-free zirconium-based amorphous alloy with high glass forming capability and preparation and application thereof Active CN109355602B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111996470A (en) * 2020-08-26 2020-11-27 燕山大学 Zirconium-based bulk amorphous alloy and preparation method thereof
US20220056566A1 (en) * 2019-04-30 2022-02-24 Oregon State University Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems
CN114657480A (en) * 2022-03-28 2022-06-24 北京科技大学 High-plasticity phase-separated Zr-based amorphous alloy and preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787501A (en) * 2010-02-05 2010-07-28 北京科技大学 Bulk metal glass composite material with stretching plasticity and work hardening capacity
CN102534437A (en) * 2011-12-15 2012-07-04 比亚迪股份有限公司 Amorphous alloy and method for preparing same
CN103911564A (en) * 2012-12-31 2014-07-09 比亚迪股份有限公司 Zr based amorphous alloy and manufacturing method thereof
CN104498844A (en) * 2014-11-18 2015-04-08 北京科技大学 Heavy size TRIP amorphous composite material and preparation method thereof
CN104745973A (en) * 2013-12-26 2015-07-01 比亚迪股份有限公司 Zr-based amorphous alloy and manufacturing method thereof
CN104745974A (en) * 2013-12-30 2015-07-01 比亚迪股份有限公司 Amorphous alloy product and preparation method thereof
CN106702292A (en) * 2016-12-12 2017-05-24 北京科技大学 N-containing Be-free Ni-free high-hardness Zr matrix body amorphous alloy and preparation method thereof
CN106756647A (en) * 2016-12-12 2017-05-31 北京科技大学 A kind of high-ductility zirconium-based bulk amorphous alloy without nickel and preparation method thereof without beryllium
CN107541682A (en) * 2016-06-29 2018-01-05 比亚迪股份有限公司 A kind of spring and preparation method thereof and for preparing its die assembly

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787501A (en) * 2010-02-05 2010-07-28 北京科技大学 Bulk metal glass composite material with stretching plasticity and work hardening capacity
CN102534437A (en) * 2011-12-15 2012-07-04 比亚迪股份有限公司 Amorphous alloy and method for preparing same
CN103911564A (en) * 2012-12-31 2014-07-09 比亚迪股份有限公司 Zr based amorphous alloy and manufacturing method thereof
CN104745973A (en) * 2013-12-26 2015-07-01 比亚迪股份有限公司 Zr-based amorphous alloy and manufacturing method thereof
CN104745974A (en) * 2013-12-30 2015-07-01 比亚迪股份有限公司 Amorphous alloy product and preparation method thereof
CN104498844A (en) * 2014-11-18 2015-04-08 北京科技大学 Heavy size TRIP amorphous composite material and preparation method thereof
CN107541682A (en) * 2016-06-29 2018-01-05 比亚迪股份有限公司 A kind of spring and preparation method thereof and for preparing its die assembly
CN106702292A (en) * 2016-12-12 2017-05-24 北京科技大学 N-containing Be-free Ni-free high-hardness Zr matrix body amorphous alloy and preparation method thereof
CN106756647A (en) * 2016-12-12 2017-05-31 北京科技大学 A kind of high-ductility zirconium-based bulk amorphous alloy without nickel and preparation method thereof without beryllium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220056566A1 (en) * 2019-04-30 2022-02-24 Oregon State University Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems
US11821064B2 (en) * 2019-04-30 2023-11-21 Oregon State University Cu-based bulk metallic glasses in the Cu—Zr—Hf—Al and related systems
CN111996470A (en) * 2020-08-26 2020-11-27 燕山大学 Zirconium-based bulk amorphous alloy and preparation method thereof
CN114657480A (en) * 2022-03-28 2022-06-24 北京科技大学 High-plasticity phase-separated Zr-based amorphous alloy and preparation method and application thereof

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