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CN102453845A - Copper-zirconium-based amorphous alloy and preparation method thereof - Google Patents

Copper-zirconium-based amorphous alloy and preparation method thereof Download PDF

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CN102453845A
CN102453845A CN2010105864789A CN201010586478A CN102453845A CN 102453845 A CN102453845 A CN 102453845A CN 2010105864789 A CN2010105864789 A CN 2010105864789A CN 201010586478 A CN201010586478 A CN 201010586478A CN 102453845 A CN102453845 A CN 102453845A
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zirconium
copper
amorphous alloy
equal
alloy
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潘碧绦
李运春
张法亮
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BYD Co Ltd
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Abstract

The invention provides a copper-zirconium-based amorphous alloy and a preparation method thereof, wherein the composition of the copper-zirconium-based amorphous alloy is shown as the following general formula: cuaZrbAlcCodAge(ii) a Wherein a, b, c, d and e are atomic percent, a is more than or equal to 35 and less than or equal to 50, b is more than or equal to 44 and less than or equal to 50, c is more than or equal to 7 and less than or equal to 10, d is more than or equal to 2 and less than or equal to 6, e is more than 0 and less than or equal to 2, and the sum of a, b, c, d and e is 100. The amorphous alloy can greatly reduce the cost under the condition of completely better mechanical property, and although the mechanical property is slightly lower than one or two properties in the prior art, the amorphous alloy can completely meet various performance requirements of the amorphous alloy in terms of comprehensive mechanical property.

Description

A kind of copper-zirconium-base amorphous alloy and preparation method thereof
Technical field
The present invention relates to a kind of Alloy And Preparation Method, relate in particular to a kind of copper-zirconium-base amorphous alloy and preparation method thereof.
Background technology
Non-crystaline amorphous metal is that the composed atom arrangement is not periodically and symmetric one type of novel alloy material.Because its special microtexture, cause them to have superior mechanics, physics, chemistry and magnetic property, like HS, high firmness, performance such as wear-resistant, corrosion-resistant.
Since earlier 1990s; Headed by the Japan and the U.S.; A series of alloying constituents have been found with strong amorphous formation ability; Wherein make the most easily with zirconium-base amorphous alloy, its critical cooling rate is in the 1K/s magnitude, can cast with method such as shrend with copper mold and be prepared into three-dimensional block materials.Recently, developed multicomponent Cu-based bulk body amorphous alloy abroad again, with respect to non-crystaline amorphous metals such as zirconium base, palladium bases, Cu-based bulk body non-crystaline amorphous metal has cheaper price and more practical value, but the amorphous formation ability of Cu-based bulk body non-crystaline amorphous metal is relatively poor.
For the problem of the amorphous formation ability difference that solves cu-based amorphous alloys and the intensity that further improves cu-based amorphous alloys, a kind of Zr-Cu-Al-Ag Al-Cu-Zn block amorphous alloy (non-crystaline amorphous metal that size reaches millimeter magnitude is called as bulk amorphous alloys) is disclosed in the prior art.This Al-Cu-Zn block amorphous alloy comprises the amorphous phase of volume(tric)fraction 50-100%, and this is that the structural formula of alloy is Zr ↓ [48] Cu ↓ [45-x] Al ↓ [7] Ag ↓ [x], and wherein x is an Ag atoms of elements percentage ratio, 1<x<10.
But, among the embodiment of foregoing invention the argentiferous content of disclosed Cu-based bulk body non-crystaline amorphous metal be 2% this during than low value, its hardness is merely 490Hv.Though the mechanics of the copper-zirconium-base amorphous alloy of the silver content that adopts during greater than 3wt% is better, the price of silver is copper or zirconium about ten times, and therefore, use is silver-colored in a large number industry in can make the non-crystaline amorphous metal cost for preparing higher.
Summary of the invention
The objective of the invention is in order to overcome the higher defective of copper-zirconium-base amorphous alloy price in the prior art, the non-crystaline amorphous metal that a kind of cost is relatively low and mechanical property is simultaneously preferable is provided.
The invention provides a kind of copper-zirconium-base amorphous alloy, the composition of this copper-zirconium-base amorphous alloy is shown in following general formula: Cu aZr bAl cCo dAg eWherein, a, b, c, d, e are atomic percent, 35≤a≤50,44≤b≤50,7≤c≤10,2≤d≤6,0<e≤2, and a, b, c, d, e sum are 100.
The present invention also provides a kind of preparation method of above-mentioned copper-zirconium-base amorphous alloy; This method is included under shielding gas atmosphere or the vacuum environment; The non-crystaline amorphous metal raw material is carried out the melting and the cooling forming of casting, it is characterized in that, said non-crystaline amorphous metal raw material general molecular formula Cu aZr bAl cCo dAg eRatio, in the formula, wherein, a, b, c, d, e are atomic percent, 35≤a≤50,44≤b≤50,7≤c≤10,2≤d≤6,0<e≤2, and a, b, c, d, e sum are 100.
The mechanical property bending strength of the copper-zirconium-base amorphous alloy that the present invention makes, elasticity of flexure strain and hardness are all preferable.Simultaneously; The silver content of the non-crystaline amorphous metal that the present invention obtains reduces with respect to prior art greatly; Contriver of the present invention finds to adopt element cobalt can partly substitute silver through a large amount of experiments, and each item mechanical property (bending strength, elasticity of flexure strain and hardness) that makes non-crystaline amorphous metal is the while preferably, and amorphous formation ability does not descend yet; And the price of cobalt is merely about 1/10th of silver; Simultaneously, the content of aluminium, zirconium, copper all need be controlled at when could realize the mechanics better performances in the narrower scope, and can also form diameter D easily is the large block amorphous bar of 3mm.Therefore, the cost of copper-zirconium-base amorphous alloy of the present invention is lower, and excellent property is applicable to industrial production in enormous quantities.In addition, the preparing method's of copper-zirconium-base amorphous alloy of the present invention condition is comparatively gentle, easily preparation.
Adopt non-crystaline amorphous metal of the present invention under the preferable fully situation of mechanical property, significantly to reduce cost in sum; Though mechanical property is lower slightly with respect to a certain of prior art or binomial performance, but mechanical property in general can satisfy each item performance requriements of production for non-crystaline amorphous metal fully.
Description of drawings
The X-ray powder diffraction figure of the sample that Fig. 1 makes for embodiment 1 and Comparative Examples 1;
Fig. 2 is the differential thermal analysis curve of embodiment 1.
Embodiment
The composition of copper-zirconium-base amorphous alloy of the present invention is shown in following general formula: Cu aZr bAl cCo dAg eWherein, a, b, c, d, e are atomic percent, 35≤a≤50,44≤b≤50,7≤c≤10,2≤d≤6,0<e≤2, and a, b, c, d, e sum are 100.
Under the preferable case, 3≤d≤5,0.5≤e≤1.5 under this preferable case, can make the excellent more copper-zirconium-base amorphous alloy of bending strength.
The preparation method of copper-zirconium-base amorphous alloy of the present invention, this method are included under shielding gas atmosphere or the vacuum environment, and the non-crystaline amorphous metal raw material is carried out the melting and the cooling forming of casting, wherein, and said non-crystaline amorphous metal raw material general molecular formula Cu aZr bAl cCo dAg e, wherein, a, b, c, d, e are atomic percent, 35≤a≤50,44≤b≤50,7≤c≤10,2≤d≤6,0<e≤2, and a, b, c, d, e sum are 100.
Wherein, used material purity is more than 99%.
Wherein, melt back at least 3 times is carried out in said melting, so that melting is even.
Among the preparation method of non-crystaline amorphous metal according to the invention, containing a spot of impurity in the said non-crystaline amorphous metal raw material to not influence of the melting of non-crystaline amorphous metal, is benchmark with the total amount of non-crystaline amorphous metal, and the content of said impurity is to get final product below the 5 atom %.Therefore, preparation method of the present invention is not high for the requirement of the purity of various raw materials yet, but material purity is high, helps the formation of non-crystaline amorphous metal.Therefore, the purity that is used to prepare the various raw materials of copper-zirconium-base amorphous alloy according to the invention is preferably more than the 99 weight %, more preferably 99-99.999 weight %.
Said shielding gas atmosphere or vacuum environment are in order to make alloy raw material in fusion process, obtain protection, to avoid oxidized.The antioxidant property of non-crystaline amorphous metal raw material of the present invention is better, and is therefore lower to the requirement of shielding gas atmosphere and vacuum environment.Said shielding gas is one or more in the neutral element gas in the periodic table of elements.The purity of said shielding gas is not less than 95 volume % and gets final product, and for example can be 95-99.9 volume %.Only need be evacuated to vacuum tightness before the feeding shielding gas in the smelting furnace is to get final product below 1000 handkerchiefs.In addition, said vacuum environment is meant that vacuum tightness is no more than 1000 handkerchiefs, is preferably the 0.1-1000 handkerchief.Vacuum tightness according to the invention is represented with absolute pressure.
The method of said melting is the melting method of various routines in this area; As long as with the abundant fusion of non-crystaline amorphous metal raw material; For example can in melting equipment, carry out melting, smelting temperature and smelting time are along with raw-material different some variations that have of used non-crystaline amorphous metal, among the present invention; Smelting temperature is preferably 1000-2700 ℃, more preferably 1200-2500 ℃; Smelting time is preferably 0.5-5 minute, more preferably 1-3 minute.Said melting equipment can be the melting equipment of routine, for example arc-melting furnace or induction melting.
The crystallized ability of non-crystaline amorphous metal of the present invention is strong, and therefore said cooling forming can adopt the casting cooling forming method of various routines in this area, for example, fused alloy material (melt) is cast in the mould, then cooling.Said casting process can be for gravity casting, inhale in casting, spray to cast, the die casting any one.Gravity casting is meant and utilizes the action of gravity of melt itself to be cast in the mould.Gravity casting realize easily, and cost is low, so the present invention preferably uses because method is simple.The concrete operation method of said casting is conventionally known to one of skill in the art.Moulding stock can be the material of 30-400W/mK (being preferably 50-200W/mK) for copper alloy, stainless steel and thermal conductivity.Mould can carry out water-cooled, oil cooling or cooled with liquid nitrogen.Refrigerative speed can be more than the 10K/s, to be preferably 10-10 4K/s.The refrigerative degree there are not special demands, as long as can be shaped to non-crystaline amorphous metal of the present invention.
In addition, preferably when adding raw material, make a in the above-mentioned general formula, b in following scope: 49≤a≤51,35≤b≤45.Under above-mentioned preferable case, the amorphous formation ability of non-crystaline amorphous metal is stronger, can obtain the better copper-zirconium-base amorphous alloy of plasticity.
Specify the present invention through embodiment below.
Embodiment 1
Present embodiment is explained copper-zirconium-base amorphous alloy provided by the invention and preparation method thereof.
With purity is that the various copper-zirconium-base amorphous alloy raw materials of 99.96 weight % drop in the arc-melting furnaces (Shenyang scientific instrument factory), and with arc melting stove evacuation (vacuum tightness is 5 handkerchiefs), the argon gas that feeds purity then and be 99.9 volume % is as shielding gas; Form the argon shield atmosphere of 0.08MPa, under 1300 ℃ of conditions, melting 3 minutes; Make the abundant fusion of copper-zirconium-base amorphous alloy raw material, melt back 3 times is in particular after the melting once; Be that the upset ingot casting repeats melting for the second time again after treating its cooling in electric arc furnace, treat its cooling after; The ingot casting that overturns again repeats melting for the third time, is to be melt back 3 times.Melt back 3 times is to guarantee that alloying constituent is even.The concrete alloy composition of composition that this embodiment uses is (atomic percent):
Cu:36.43;Zr:49;Al:10;Co:3.07;Ag:1.5。
Then the method for fused alloy sample through gravity casting is cast in the copper mold, and with 10 3The speed of cooling of K/s is carried out the water cooled copper mould cooling, forms the copper-zirconium-base amorphous alloy sample A1 that is of a size of 3 millimeters of Φ, 20 millimeters of length.Ultimate analysis shows, this copper-zirconium-base amorphous alloy sample A1 consists of Cu 36.43Zr 49Al 10Co 3.07Ag 1.5
Comparative Examples 1
Method according to embodiment 1 prepares copper-zirconium-base amorphous alloy, and the concrete alloy composition of composition that this Comparative Examples is used is (atomic percent):
Cu:43;Zr:47;Al:7;Ag:3。
Finally obtain non-crystaline amorphous metal sample D1.Ultimate analysis shows, this copper-zirconium-base amorphous alloy sample D1 consists of Cu 43Zr 47Al 7Ag 3
Embodiment 2
Method according to embodiment 1 prepares copper-zirconium-base amorphous alloy, and different is that the concrete alloy composition of composition that this embodiment uses is (atomic percent):
Cu:42;Zr:45;Al:8;Co:4;Ag:1。
Finally obtain non-crystaline amorphous metal sample A2.Ultimate analysis shows, this copper-zirconium-base amorphous alloy sample A2 consists of Cu 42Zr 45Al 8Co 4Ag 1
Embodiment 3
Method according to embodiment 1 prepares copper-zirconium-base amorphous alloy, and different is that the concrete alloy composition of composition that this embodiment uses is (atomic percent):
Cu:42;Zr:45;Al:9;Co:2;Ag:2。
Finally obtain non-crystaline amorphous metal sample A3.Ultimate analysis shows, this copper-zirconium-base amorphous alloy sample A2 consists of Cu 42Zr 45Al 9Co 2Ag 2
Embodiment 4
Method according to embodiment 1 prepares copper-zirconium-base amorphous alloy, and different is that the concrete alloy composition of composition that this embodiment uses is (atomic percent):
Cu:42.5;Zr:44;Al:7;Co:6;Ag:0.5。
Finally obtain non-crystaline amorphous metal sample A4.Ultimate analysis shows, this copper-zirconium-base amorphous alloy sample A4 consists of Cu 42.5Zr 44Al 7Co 6Ag 0.5
Embodiment 5
Method according to embodiment 1 prepares copper-zirconium-base amorphous alloy, and different is,
Cu:36.5;Zr:50;Al:7;Co:6;Ag:0.5。
Finally obtain non-crystaline amorphous metal sample A5.Ultimate analysis shows, this copper-zirconium-base amorphous alloy sample A5 consists of Cu 36.5Zr 50Al 7Co 6Ag 0.5
According to following testing method embodiment and Comparative Examples test result are carried out test analysis:
1, XRD analysis
The copper-zirconium-base amorphous alloy sample that the foregoing description 1-5 is made carries out the XRD powder diffraction analysis respectively on model is the x-ray powder diffraction instrument of D-MAX2200PC, to judge whether alloy is amorphous.The condition of X-ray powder diffraction comprises with the copper target emanation; Incident wavelength
Figure BSA00000384331200071
acceleration voltage is 40 kilovolts; Electric current is 20 milliamperes; Adopt step-scan, scanning step is 0.04 °, and the result is as shown in Figure 1.
From Fig. 1, observe and can know: the diffraction spectra A1 of non-crystaline amorphous metal sample has only a diffuse scattering peak; And the diffraction spectra A of Comparative Examples 1 has significantly crystallization peak; The non-crystaline amorphous metal that Comparative Examples 1 preparation is described crystal occurred in diameter is the bar of 3mm; Therefore, the amorphous formation ability of Comparative Examples 1 is significantly less than embodiments of the invention 1.Contriver of the present invention tests (not shown) to non-crystaline amorphous metal sample A2-A5 through XRD; Be and disperse the peak; In the effective resolution of X-ray diffractometer, do not observe any crystallization peak; Explain that embodiments of the invention 1-5 all can form the amorphous bar that diameter is 3mm, the large block amorphous formation ability of technical scheme of the present invention is very good.
2, DSC DTA
The non-crystaline amorphous metal sample A1-A5 that respectively embodiment 1-5 is obtained is in simultaneous thermal analysis appearance (German NETZSCH company; STA449C Jupiter) carries out DTA on; Test condition is included under the nitrogen protection, with 20 ℃/minute speed elevated temperature, to detect glass transformation temperature (Tg), crystallization temperature (Tx) and the fusing point (Tm) of non-crystaline amorphous metal; The result of A1 is as shown in Figure 2, and its thermodynamic data is listed in table 1.
3, three-point bending experiment
Method according to GB/T14452-93; Test on the non-crystaline amorphous metal sample A1-A5 that respectively embodiment 1-5 and Comparative Examples 1 is obtained, the experimental machine (newly thinking carefully company) that D1 at tonnage is 1 ton; 50 millimeters of spans; Loading velocity is 0.5 mm/min, obtains bending strength, elasticity of flexure strain, and the result is as shown in table 1.
4, hardness test
The non-crystaline amorphous metal sample A1-A5, the D1 that respectively embodiment 1-5 and Comparative Examples 1 are obtained carry out hardness test on Vickers' hardness test machine (Micro Hardness Text Hv1000); The condition of hardness test comprises that pressure head weight is 200 grams; Loading time is 10 seconds; Each sample is got three numerical value, gets its arithmetical av at last, and test result is as shown in table 1.
Table 1
Figure BSA00000384331200081
Can find out that from table 1 mechanical property of embodiments of the invention and Comparative Examples is compared basic identical, can satisfy fully in the production requirement about each item mechanical property of non-crystaline amorphous metal, and the while adopted less silver with respect to Comparative Examples, cost is lower.

Claims (10)

1. a copper-zirconium-base amorphous alloy is characterized in that, the composition of this copper-zirconium-base amorphous alloy is shown in following general formula: CuaZrbAlcCodAge; Wherein, a, b, c, d, e are atomic percent, 35≤a≤50,44≤b≤50,7≤c≤10,2≤d≤6,0<e≤2, and a, b, c, d, e sum are 100.
2. alloy according to claim 1, wherein, 3≤d≤5,0.5≤e≤1.5.
3. the preparation method of the described copper-zirconium-base amorphous alloy of claim 1, this method is included under shielding gas atmosphere or the vacuum environment, and the non-crystaline amorphous metal raw material is carried out the melting and the cooling forming of casting, and it is characterized in that, said non-crystaline amorphous metal raw material general molecular formula Cu aZr bAl cCo dAg e, wherein, a, b, c, d, e are atomic percent, 35≤a≤50,44≤b≤50,7≤c≤10,2≤d≤6,0<e≤2, and a, b, c, d, e sum are 100.
4. method according to claim 3, wherein, used material purity is more than 99%.
5. method according to claim 3, wherein, melt back at least 3 times is carried out in said melting.
6. method according to claim 3, wherein, the condition of said melting comprises that smelting temperature is 1000-2700 ℃, smelting time is 0.5-5 minute.
7. method according to claim 3, wherein, during said cooling forming, rate of cooling is more than the 10K/s.
8. method according to claim 3, wherein, said shielding gas is one or more in the neutral element gas in the periodic table of elements.
9. method according to claim 3, wherein, the vacuum tightness of said vacuum environment is the 0.1-1000 handkerchief.
10. method according to claim 3, wherein, the method for said casting is a gravity casting.
CN2010105864789A 2010-12-10 2010-12-10 Copper-zirconium-based amorphous alloy and preparation method thereof Pending CN102453845A (en)

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CN106244946A (en) * 2016-09-27 2016-12-21 北京科技大学 A kind of high-strength plasticity zirconium-base amorphous alloy containing molybdenum and preparation method
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
CN114561604A (en) * 2022-01-18 2022-05-31 中国人民解放军陆军装甲兵学院 Copper-zirconium-based amorphous powder for repairing multiple damages, coating and preparation method
CN114559048A (en) * 2022-03-15 2022-05-31 深圳大学 Preparation method of copper-based composite amorphous powder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106244946A (en) * 2016-09-27 2016-12-21 北京科技大学 A kind of high-strength plasticity zirconium-base amorphous alloy containing molybdenum and preparation method
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CN114559048A (en) * 2022-03-15 2022-05-31 深圳大学 Preparation method of copper-based composite amorphous powder
CN114559048B (en) * 2022-03-15 2024-05-07 深圳大学 Preparation method of copper-based composite amorphous powder

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Application publication date: 20120516