CN101003884A - Zirconium based amorphous alloy - Google Patents

Zirconium based amorphous alloy Download PDF

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Publication number
CN101003884A
CN101003884A CN 200710063357 CN200710063357A CN101003884A CN 101003884 A CN101003884 A CN 101003884A CN 200710063357 CN200710063357 CN 200710063357 CN 200710063357 A CN200710063357 A CN 200710063357A CN 101003884 A CN101003884 A CN 101003884A
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alloy
metal bar
amorphous
amorphous metal
amorphous alloy
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CN 200710063357
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CN100569985C (en
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张涛
周樵
门华
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Shenzhen xinkailai Technology Co.,Ltd.
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Beihang University
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Abstract

This invention provides a kind of corrosion-resistant Zr-based amorphous alloys, whose composition is Zr55-xAl20Co25Erx, wherein x is an integer of 0-8. The alloys have such advantages as high amorphous formation ability, high strength, high toughness, good corrosion resistance, and easy production. Besides, the alloys do not contain such elements as Ni and Be that are harmful to human bodies, thus can be widely used as biomaterials, sports products and medical devices.

Description

A kind of Zirconium based amorphous alloy
Technical field
The present invention relates to amorphous alloy, particularly a kind of Zirconium based amorphous alloy.
Background technology
Bulk amorphous alloys is because of its unique microtexture, have crystal alloy incomparable mechanical property, as high strength, high rigidity, snappiness, high fracture toughness property and anti-corrosion, wear resistance, have huge potential application foreground at space flight, aviation field.But, because the preparation of non-crystaline amorphous metal needs 0.1～10 5The K/s speed of cooling, for a long time, its size range only is confined to band, filament and powder, and therefore the application of non-crystaline amorphous metal is very restricted.
The Zr base amorphous alloy has been successfully used to prepare golf club head, tennis racket and space flight solar wind collector and some other products with its high amorphous formation ability, good performance.Typical system has Zr-Ti-Ni-Cu-Be, Zr-Al-Ni-Cu-RE (rare earth), Zr-Al-Co, amorphous alloys such as Zr-Al-Ni-Cu.These amorphous alloys all have higher amorphous formation ability, critical size reaches tens even tens millimeters, but their breaking tenacity is starkly lower than cu-based amorphous alloys, and all contain mostly the deleterious element Ni of biology, Be, this has just limited its application on biomaterial, medical device and structured material greatly.Therefore, developing the breaking tenacity height, viscous deformation is good, solidity to corrosion is good and does not conform to bulk pick base noncrystal alloy material to biological harmful element, has been the inexorable trend of the development that pick base amorphous can widespread use.
Summary of the invention
One of purpose of the present invention provide a kind of can form large block amorphous, have a higher breaking tenacity and not containing again to the deleterious element Ni of biology, Be and amorphous alloy with good anti-corrosion, be specially: a kind of Zirconium based amorphous alloy is characterized in that the expression formula of alloying constituent is (atom number %): Zr 55-xAl 20Co 25Er x, wherein x is 0,1,2,3,4,5,6,7 or 8.
Zirconium based amorphous alloy of the present invention is 4 or 6 for good with X.
Unless it is clearly refer else, used herein: omnipotent test machine (mechanical testing system) hereinafter to be referred as having following implication: MTS; d Max: amorphous alloy rod critical diameter; T g: glass transformation temperature; T x: Tc; Δ T x: the interval Δ T of supercooled liquid x(=T x-T g); σ y: yield strength; σ f: breaking tenacity; ε p: amount of plastic deformation; Φ: the diameter of amorphous alloy rod.
Realize technical scheme of the present invention:
Zirconium based amorphous alloy of the present invention is prepared from by following method:
Step 1, take by weighing each element
Calculating each associated element wt by required atom number takes by weighing;
Step 2, melting system Zr-Al-Co-Er mother alloy
With step 1 claim desired raw material put into vacuum smelting furnace, regulate suction to 5 * 10 -3Pa charges into argon shield gas, and argon pressure is 0.05MPa; Regulate 1000～1600 ℃ of electric current 15～25A, smelting temperatures; Furnace cooling takes out the Zr-Al-Co-Er mother alloy behind smelting time 5～10min;
Step 3, system Zr-Al-Co-Er non-crystaline amorphous metal bar
The mother alloy that step 2 is made is put into the induction furnace of quick solidification apparatus, regulates suction to 5 * 10 -3Pa charges into argon shield gas, and argon pressure is 0.05MPa; Regulate 800～1000 ℃ of electric current 2～10A, temperature sensors; Spurt in the copper mold behind smelting time 2～5min, and promptly make Zr-Al-Co-Er non-crystaline amorphous metal bar with the copper mold cooling.
Zr-Al-Co-Er non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm with making tests its compression mechanical property, and the compression mechanical property of material adopts the MTS testing of equipment.This Zr base noncrystal alloy system not only has higher breaking tenacity 2000MPa～2240Mpa, and also shows bigger viscous deformation when x=4, and the amount of plastic deformation maximum can reach 2%.
Table 1 shows the thermodynamic property and the mechanical property of the part amorphous alloy rod of being cast.The supercooled liquid of Zr base amorphous alloy of the present invention has higher thermostability, the interval Δ T of supercooled liquid x(=T x-T g)＞45 K, wherein the wideest Δ T xBe 68 K, T g: glass transformation temperature, T x: Tc.Critical size Φ＞the 6mm of the amorphous alloy that forms, Φ are the diameter of amorphous alloy rod.The compressed rupture strength of described alloy can reach more than the 2240MPa, the compressive plastic deformation amount can reach more than 0.9%, do not contain harmful element (Ni, Be) have high strength and high tenacity simultaneously again, be easy to produce, can be widely used in making various structured materials, sports equipment, biomaterial and medical device.
Table 1
Alloy d max (mm) T g(K) T x(K) ΔT x (K) σ y (MPa) σ f (MPa) ε p (％)
Zr 55Al 20Co 25 3 763 825 62 1800 1930 0.2
Zr 54Al 20Co 25Er 1 3 762 827 65 - - -
Zr 53Al 20Co 25Er 2 3 752 820 68 1940 2100 0.9
Zr 52Al 20Co 25Er 3 3 753 813 60 - - -
Zr 51Al 20Co 25Er 4 4 753 811 58 1920 2140 2
Zr 50Al 20Co 25Er 5 5 745 807 62 - - -
Zr 49Al 20Co 25Er 6 6 734 792 58 1940 2240 0.9
Zr 48Al 20Co 25Er 7 5 748 801 53 - - -
Zr 55Al 20Co 25Er 8 5 752 797 45 1950 2220 0.2
The present invention is further illustrated below by embodiment, but the present invention is not limited only to these embodiment.
Embodiment
Embodiment 1:
Preparation Zr 49Al 20Co 25Er 6The non-crystaline amorphous metal bar
Step 1: press Zr 49Al 20Co 25Er 6The chemical ingredients proportioning is prepared burden.
Mol ratio according to Zr: Al: Co: Er is 49: 20: 25: 6 proportional meter is calculated each associated element wt, and adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Co and 99.9% rare earths material Er prepare burden.
Step 2: system Zr 49Al 20Co 25Er 6Mother alloy
The batching of step 1 is put into vacuum smelting furnace;
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1100 ℃ of smelting temperatures;
Take out behind the furnace cooling behind the smelting time 5min;
Step 3: system Zr 49Al 20Co 25Er 6The non-crystaline amorphous metal bar
The Zr that step 2 is made 49Al 20Co 25Er 6Mother alloy is put into the induction furnace of quick solidification apparatus,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 2-10A, 850 ℃ of temperature sensors;
Be injected into behind the smelting time 2min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～6mm), with making Zr after the copper mold cooling 49Al 20Co 25Er 6The non-crystaline amorphous metal bar.This Zr 49Al 20Co 25Er 6Alloy has good amorphous formation ability, and maximum critical size is 6mm; With the Zr that makes 49Al 20Co 25Er 6Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1940MPa, and breaking tenacity is 2240MPa, and amount of plastic deformation is 0.9%, and other performances are as shown in table 1.
Embodiment 2:
Preparation Zr 51Al 20Co 25Er 4The non-crystaline amorphous metal bar
Step 1: press Zr 51Al 20Co 25Er 4The chemical ingredients proportioning is prepared burden;
Adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Co and 99.9% rare earths material Er, be 51: 20: 25 according to the mol ratio of Zr: Al: Co: Er: 4 ratio is prepared burden, and other steps are with embodiment 1.
Step 2: system Zr 51Al 20Co 25Er 4Mother alloy
The described batching that step 1 makes is put into vacuum smelting furnace,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1100 ℃ of smelting temperatures;
Take out behind the furnace cooling behind the smelting time 5min;
Step 3: system Zr 49Al 20Co 25Er 6The non-crystaline amorphous metal bar
The described Zr that step 2 is made 51Al 20Co 25Er 4Mother alloy is put into the induction furnace of quick solidification apparatus,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 2-10A, 850 ℃ of temperature sensors;
Be injected into behind the smelting time 2min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～6mm), with making Zr after the copper mold cooling 51Al 20Co 25Er 4The non-crystaline amorphous metal bar.This Zr 51Al 20Co 25Er 4Alloy has good amorphous formation ability, and maximum critical size is 4mm; With the Zr that makes 51Al 20Co 25Er 4Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1920MPa, and breaking tenacity is 2140MPa, and amount of plastic deformation is 2%, and other performances are as shown in table 1.
Embodiment 3:
Preparation Zr 55Al 20Co 25Er 8The non-crystaline amorphous metal bar
Step 1: press Zr 55Al 20Co 25Er 8The chemical ingredients proportioning is prepared burden
Adopting purity is 99.9% Zr, 99.9% Al, and 99.9% Co and 99.9% rare earths material Er, be 55: 20: 25 according to the mol ratio of Zr: Al: Co: Er: 8 ratio is prepared burden, and other steps are with embodiment 1.
Step 2: system Zr 55Al 20Co 25Er 8Mother alloy
The described batching that step 1 makes is put into vacuum smelting furnace,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1100 ℃ of smelting temperatures;
Take out behind the furnace cooling behind the smelting time 5min;
Step 3: system Zr 49Al 20Co 25Er 6The non-crystaline amorphous metal bar
The described Zr that step 2 is made 51Al 20Co 25Er 4Mother alloy is put into the induction furnace of quick solidification apparatus,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 2-10A, 850 ℃ of temperature sensors;
Be injected into behind the smelting time 2min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～6mm), with making Zr after the copper mold cooling 55Al 20Co 25Er 8The non-crystaline amorphous metal bar.This Zr 55Al 20Co 25Er 8Alloy has good amorphous formation ability, and maximum critical size is 5mm; With the Zr that makes 55Al 20Co 25Er 8Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1950MPa, and breaking tenacity is 2220MPa, and amount of plastic deformation is 0.2%, and other performances are as shown in table 1.
Embodiment 4:
Preparation Zr 55Al 20Co 25The non-crystaline amorphous metal bar
Step 1: press Zr 55Al 20Co 25The chemical ingredients proportioning is prepared burden
Adopting purity is 99.9% Zr, and 99.9% Al and 99.9% Co are that 55: 20: 25 ratio is prepared burden according to the mol ratio of Zr: Al: Co, and other steps are with embodiment 1.
Step 2: system Zr 55Al 20Co 25Mother alloy
The described batching that step 1 makes is put into vacuum smelting furnace,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 20A, 1100 ℃ of smelting temperatures;
Take out behind the furnace cooling behind the smelting time 5min;
Step 3: system Zr 55Al 20Co 25The non-crystaline amorphous metal bar
The described Zr that step 2 is made 55Al 20Co 25Mother alloy is put into the induction furnace of quick solidification apparatus,
Regulate suction to 5 * 10 -3Pa charges into 0.05MPa argon shield gas then;
Regulate electric current 2-10A, 850 ℃ of temperature sensors;
Be injected into behind the smelting time 2min in the copper mold (selecting the internal recess diameter respectively is the mould of 2～6mm), with making Zr after the copper mold cooling 55Al 20Co 25The non-crystaline amorphous metal bar.This Zr 55Al 20Co 25Alloy has good amorphous formation ability, and maximum critical size is 3mm; With the Zr that makes 55Al 20Co 25Non-crystaline amorphous metal bar intercepting Φ 2mm * 4mm tests its compression mechanical property, and yield strength is 1800MPa, and breaking tenacity is 1930MPa, and amount of plastic deformation is 0.2%, and other performances are as shown in table 1.

Claims (2)

1, a kind of Zirconium based amorphous alloy is characterized in that the expression formula of alloying constituent is (atom number %): Zr 55-xAl 20Co 25Er X, wherein x is 0,1,2,3,4,5,6,7 or 8.
2, a kind of Zirconium based amorphous alloy as claimed in claim 1 is characterized in that: described X is 4 or 6.
CNB2007100633574A 2007-01-10 2007-01-10 A kind of Zirconium based amorphous alloy Active CN100569985C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102392200A (en) * 2011-11-14 2012-03-28 北京航空航天大学 High content zirconium plastic Zr-Al-Fe bulk amorphous alloy and preparation method thereof
CN102517525A (en) * 2011-12-31 2012-06-27 北京航空航天大学 Copper mould casting and ironing combined method for preparing corrosion-resistant Zr-based amorphous alloy
CN103484800A (en) * 2013-09-10 2014-01-01 黄利敏 Zirconium-based amorphous alloy and preparation method thereof
CN107058912A (en) * 2017-03-30 2017-08-18 福建工程学院 Zr base block amorphous alloys containing precious metal element and preparation method thereof
CN113046658A (en) * 2021-03-11 2021-06-29 株洲宜安新材料研发有限公司 Amorphous alloy preparation process for weapon manufacturing

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102392200A (en) * 2011-11-14 2012-03-28 北京航空航天大学 High content zirconium plastic Zr-Al-Fe bulk amorphous alloy and preparation method thereof
CN102392200B (en) * 2011-11-14 2013-06-05 北京航空航天大学 High content zirconium plastic Zr-Al-Fe bulk amorphous alloy and preparation method thereof
CN102517525A (en) * 2011-12-31 2012-06-27 北京航空航天大学 Copper mould casting and ironing combined method for preparing corrosion-resistant Zr-based amorphous alloy
CN103484800A (en) * 2013-09-10 2014-01-01 黄利敏 Zirconium-based amorphous alloy and preparation method thereof
CN103484800B (en) * 2013-09-10 2015-12-09 黄利敏 A kind of zirconium-base amorphous alloy and preparation method thereof
CN107058912A (en) * 2017-03-30 2017-08-18 福建工程学院 Zr base block amorphous alloys containing precious metal element and preparation method thereof
CN113046658A (en) * 2021-03-11 2021-06-29 株洲宜安新材料研发有限公司 Amorphous alloy preparation process for weapon manufacturing

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