CN102703841A - Method for improving bending ductility of zirconium-based bulk amorphous alloy - Google Patents
Method for improving bending ductility of zirconium-based bulk amorphous alloy Download PDFInfo
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- CN102703841A CN102703841A CN201210163602XA CN201210163602A CN102703841A CN 102703841 A CN102703841 A CN 102703841A CN 201210163602X A CN201210163602X A CN 201210163602XA CN 201210163602 A CN201210163602 A CN 201210163602A CN 102703841 A CN102703841 A CN 102703841A
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Abstract
The invention discloses a method for improving the bending ductility of zirconium-based bulk amorphous alloy. The method comprises the steps of firstly preparing an original master alloy cast ingot; secondly fining master alloy cast ingot solidified structure; and thirdly preparing the zirconium-based bulk amorphous alloy. The method ensures that the disorder degree and the free volume content of corresponding bulk amorphous alloy are obviously increased by controlling the master alloy cast ingot solidified structure, thereby achieving the purpose of improving the bending ductility of zirconium-based bulk amorphous alloy, and having the characteristics of simple structure and low cost.
Description
Technical field
The present invention relates to the technology of preparing of block amorphous alloy, be specially a kind of method of improving the zirconium-based bulk amorphous alloy bending ductility through the control microtexture.
Background technology
When alloy melt solidified with the mode of growing up with the crystal forming core, the atomic arrangement mode must change, and promptly the short range order atomic configuration from continuous variation becomes the long-range order atomic configuration corresponding with crystalline structure and composition.Atomic configuration these variations in process of setting are all relevant with atomic diffusion, for the alloy of any one composition, when solidifying cooling rate when enough high, just can suppress the carrying out of spreading and form non-crystaline amorphous metal (metallic glass).
Zirconium-based bulk amorphous alloy has higher glass forming ability, is one type of very promising structured material.Yet some early stage results of study find that zirconium-based bulk amorphous alloy is the hard brittle material of a quasi-representative, and at ambient temperature, they not only show almost nil stretching plastic and limited compression plasticity, and do not have tangible bending ductility.But some nearest results of study find to improve through the control microtexture plasticity of zirconium-based bulk amorphous alloy.Such as, in matrix, introduce nanocrystalline or low-temperature annealing causes in the matrix occurring the inhomogeneous equal compression plasticity that can improve alloy of nano level structure through the low temperature spray to cast; Also can in noncrystal substrate, introduce a large amount of equally distributed shear zones, thereby improve the bending ductility of alloy through rolling deformation.Though aforesaid method has improved the plasticity of zirconium-based bulk amorphous alloy to a certain extent, significant limitation is also arranged, or operating procedure relative complex, loaded down with trivial details, or nanocrystalline form, distribution and quantity are difficult to effectively control, therefore are difficult to extensively popularize.
Correlative study work shows that the plasticity of block amorphous alloy and the degree of disorder of microtexture and free volume content are closely related.The degree of disorder of microtexture and free volume content are high more, and plasticity is just good more.Therefore, can be through the degree of disorder that increases microtexture and the plasticity that free volume content improves non-crystaline amorphous metal.As everyone knows, non-crystaline amorphous metal is the quick refrigerative product of liquid alloy, can think the liquid of " freezing ", and its atomic configuration must be relevant with corresponding Liquid Structure.Existing work shows that the solidified structure of mother alloy ingot and the microtexture of non-crystaline amorphous metal have confidential relation, therefore can reach the purpose of improving amorphous alloy plasticity through the solidified structure of control mother alloy ingot.
Summary of the invention
The object of the present invention is to provide a kind of method of improving zirconium-based bulk amorphous alloy plasticity, this method technology cost is low and simple and easy to do, can obviously improve the bending ductility of block amorphous alloy.
Technical solution of the present invention is following:
A kind of method of improving the zirconium-based bulk amorphous alloy bending ductility is characterized in that, the concrete steps of this method are following:
The first step, the preparation of original mother alloy ingot: the interior fusing of water jacketed copper crucible that required pure metal (purity is not less than 99.9wt%) is placed vacuum arc melting furnace by the alloy nominal composition.Fusion current is 200 peaces, and melting atmosphere is the high-purity argon gas through the molten titanium oxygen consumption, and the melting once time is 60 seconds; After accomplishing melting once, turn over ingot casting and carry out melting again, melt back 4 times, even with the chemical ingredients that guarantees mother alloy ingot;
Second step; The refinement of mother alloy ingot solidified structure: the original mother alloy ingot that the first step is obtained is crushed to a plurality of fritters; The fritter alloy of certain mass is placed in the water jacketed copper crucible again, the melting electric current be 200 peaces with certain electric arc height situation under melt back 3 ~ 6 times;
The 3rd step, the preparation of zirconium-based bulk amorphous alloy: the mother alloy ingot refuse with second step obtained, utilize the absorbing and casting device in the electric arc furnace, the melt suction water cooled copper mould with mother alloy obtains the high zirconium-based bulk amorphous alloy of bending ductility.
The method mechanism of improving the zirconium-based bulk amorphous alloy bending ductility provided by the invention is: after the original mother alloy ingot melt back repeatedly, the degree of disorder and the free volume content of the block amorphous alloy microtexture that obtains significantly increase.Highly unordered microtexture is being introduced more rheology zone simultaneously, also helps in entire scope, occurring intensive shearing transition events, to such an extent as to the viscous deformation of more disperse before fracture suddenly takes place, occurs.And free volume mainly influences the plasticity of non-crystaline amorphous metal through following dual mode.On the one hand, the higher position of free volume content has lower intensity usually, and very sensitive to loading stress.The softening zone that is pre-existing in can be thought in these positions.These zones possibly cause stress concentration with the difference of peripheral region elastic performance in plastic history, help the forming core of shear zone.On the other hand, high free volume content means the increase of atomic diffusion ability.High atomic diffusion ability helps relieve stresses to be concentrated, thereby prevents to occur too early the expansion that crackle also can stop crackle.This just makes non-crystaline amorphous metal before fracture, obtain more viscous deformation.
In vacuum arc fumace, with the original mother alloy ingot melt back of certain mass repeatedly, make the remarkable refinement of its solidified structure; Utilize these ingot castings to prepare flaky block amorphous alloy through copper mold casting.Compare with the block amorphous alloy that original mother alloy ingot obtains, the degree of disorder and the free volume content of the block amorphous alloy microtexture that obtains after the melt back repeatedly significantly increase, and flexural displacement also significantly increases.
The advantage that the present invention has is: 1, process method of the present invention is simple, does not need the input of specific installation, in general vacuum arc melting furnace, can realize, and have significant effect.2, the present invention is through the control to the mother alloy ingot solidified structure; The degree of disorder and the free volume content of respective masses non-crystaline amorphous metal microtexture are significantly increased; Thereby reach the purpose of improving existing amorphous alloy plasticity; And the man power and material who does not need labor develops new block amorphous alloy composition, has avoided a large amount of cut-and-try works, and in actually operating, realizes more easily.
Description of drawings
Fig. 1 is the Zr of mother alloy ingot through obtaining behind the different melting number of times
55Al
10Ni
5Cu
30The X-ray spectrum of block amorphous alloy.
Fig. 2 is the Zr of mother alloy ingot through obtaining behind the different melting number of times
55Al
10Ni
5Cu
30The DSC curve of block amorphous alloy, its rate of heating are 20 K/ minutes.
Fig. 3 a-b is the Zr of mother alloy ingot through obtaining behind the different melting number of times
55Al
10Ni
5Cu
30The high-resolution-ration transmission electric-lens photo of block amorphous alloy.
Fig. 4 a-b is the Zr of mother alloy ingot through obtaining behind the different melting number of times
55Al
10Ni
5Cu
30Stress in bending-the displacement curve of block amorphous alloy.
Embodiment
The present invention only need significantly increase the degree of disorder of respective masses non-crystaline amorphous metal microtexture and free volume content through the solidified structure of control mother alloy ingot, can reach the purpose of improving existing amorphous alloy plasticity.Below in conjunction with embodiment the inventive method is done further explanation, but should not limit protection scope of the present invention with this.
Zr
55Al
10Ni
5Cu
30The improvement of block amorphous alloy bending ductility:
Embodiment 1
(1) Zr, Al, Ni, Cu component that purity are not less than 99.9wt% by molar weight than after preparing for 55:10:5:30; Put into the water jacketed copper crucible of vacuum arc melting furnace; Under the high-purity argon atmosphere protection of melted pure titanium oxygen consumption, utilize electric arc that it is carried out melt back.Fusion current is 200 peaces, and the melting once process was advisable with 60 seconds.After accomplishing melting once, turn over ingot casting and carry out melting again.In order to prevent component segregation, general melt back 4 times obtains original mother alloy ingot.
(2) original mother alloy ingot is crushed to fritter; Be that the fritter alloy of 9 grams places in the water jacketed copper crucible fusing again (the melting electric current is 100 peaces with quality then; Smelting time is 10 seconds), utilize the absorbing and casting device (pressure difference is 1 normal atmosphere) in the electric arc furnace then, the melt of the original mother alloy ingot of equal in quality is sucked water cooled copper mould; Obtaining thickness is the sheet block amorphous alloy of 1 mm, representes with R0.Adopting then changes sawing at a slow speed and cuts, and obtains being of a size of 1 ' 3 ' 40 mm
3Bend specimen.
(1) step (1) with embodiment 1 is identical.
(2) original mother alloy ingot is crushed to fritter; Then with quality be 9 the gram the fritter alloy place in the water jacketed copper crucible again; Select certain melting electric current (200 peace) and electric arc height (tungsten electrode and alloy melt surface height; Can cover bath surface fully with electric arc is advisable), melt back 3 times obtains mother alloy ingot.
(3) mother alloy ingot that step (2) is obtained places fusing in the water jacketed copper crucible again, and (the melting electric current is 100 peaces; Smelting time is 10 seconds); Utilize the absorbing and casting device (pressure difference is 1 normal atmosphere) in the electric arc furnace then; The melt of the original mother alloy ingot of equal in quality is sucked water cooled copper mould, and obtaining thickness is the sheet block amorphous alloy of 1 mm, representes with R3.Adopting then changes sawing at a slow speed and cuts, and obtains being of a size of 1 ' 3 ' 40 mm
3Bend specimen.
Embodiment 3
(1) step (1) with embodiment 1 is identical.
(2) original mother alloy ingot is crushed to fritter; Then with quality be 9 the gram the fritter alloy place in the water jacketed copper crucible again; Select certain melting electric current (200 peace) and electric arc height (tungsten electrode and alloy melt surface height; Can cover bath surface fully with electric arc is advisable), melt back 6 times obtains mother alloy ingot.
(3) mother alloy ingot that step (2) is obtained places fusing in the water jacketed copper crucible again, and (the melting electric current is 100 peaces; Smelting time is 10 seconds); Utilize the absorbing and casting device (pressure difference is 1 normal atmosphere) in the electric arc furnace then; The melt of the original mother alloy ingot of equal in quality is sucked water cooled copper mould, and obtaining thickness is the sheet block amorphous alloy of 1 mm, representes with R6.Adopting then changes sawing at a slow speed and cuts, and obtains being of a size of 1 ' 3 ' 40 mm
3Bend specimen.
Table 1 is that embodiment 1, embodiment 2 and embodiment 3 samples are carried out the three-point bending test, and the fulcrum span is 20 mm, and the pressure head gait of march is 0.64 mm/min.
The result shows, along with the increase of remelting number of times, Zr
55Al
10Ni
5Cu
30The bending ductility of block amorphous alloy significantly improves.
Embodiment 1 adopts traditional method to prepare Zr
55Al
10Ni
5Cu
30Block amorphous alloy, embodiment 2 and 3 are respectively to adopt the inventive method to prepare Zr
55Al
10Ni
5Cu
30Block amorphous alloy, its bending ductility significantly improves.X-ray diffraction as shown in Figure 1 (XRD) spectrum can prove that R0 and R6 sample are non-crystalline state completely.Fig. 2 is the DSC curve of R0 and R6 sample, and as can be seen from the figure, two samples have identical glass transformation temperature (T
g), but having higher crystallization, R6 begins temperature (T
x), crystallization peak temperature (T
p), structural relaxation enthalpy (Δ H
r) and crystallization enthalpy (Δ H
c), concrete outcome sees table 2 for details.
Table 2
| Sample | T g(K) | T x(K) | T p(K) | ?ΔH r(J/g) | ΔH c(J/g) |
| R0 | 675 | 761 | 764.4 | ?4.4 | 53.2 |
| R6 | 675 | 764 | 767.8 | ?5.6 | 56.3 |
This just explains that R6 has the higher microtexture degree of disorder and free volume content than R0.Fig. 3 is the high-resolution-ration transmission electric-lens photo of R0 and R6 sample; As can be seen from the figure; This explanation R0 and R6 sample are non-crystal structure completely, find but further observe, and the R0 sample (roll into a ball bunch by the medium-range order that Fig. 3 exists some diameters to be about 2 nm in a); Also have some local orders group bunch in the R6 sample (Fig. 3 b), but their size reduces obviously.This further illustrates the R6 sample and has the higher microtexture degree of disorder.
Fig. 4 is the stress in bending-displacement curve of R0 and R6 sample, and the result shows that the average yield stress of R6 sample (Fig. 4 b) is 2599 MPa, greater than R0 sample (Fig. 4 2440 MPa a); The maximum stress in bend of two samples is obviously difference not, and their MV is about 3100 MPa; The Young's modulus of two samples is also almost as broad as long.Very meaningfully, along with the increase of mother alloy ingot remelting number of times, flexural displacement significantly increases.The R0 sample ruptures when flexural displacement is 4 ~ 5 mm basically, and the R6 sample then shows good plastic deformation ability, when flexural displacement reaches 10 mm (maximum permissible value of test set), does not also rupture.
Zr
65Al
7.5Cu
17.5Ni
10The improvement of block amorphous alloy plasticity:
Embodiment 4
(1) with purity be not less than 99.9wt% Zr, Al, Cu, Ni component by molar weight than after preparing for 65:7.5:17.5:10; Put into the water jacketed copper crucible of vacuum arc melting furnace; Under the high-purity argon atmosphere protection of melted pure titanium oxygen consumption, utilize electric arc that it is carried out melt back.Fusion current is 200 peaces, and the melting once process was advisable with 60 seconds.After accomplishing melting once, turn over ingot casting and carry out melting again.In order to prevent component segregation, general melt back gets final product for 4 times.
(2) step (2) with embodiment 1 is identical
(1) Zr, Al, Cu, Ni component that purity are not less than 99.9wt% by molar weight than after preparing for 65:7.5:17.5:10; Put into the water jacketed copper crucible of vacuum arc melting furnace; Under the high-purity argon atmosphere protection of melted pure titanium oxygen consumption, utilize electric arc that it is carried out melt back.Fusion current is 200 peaces, and the melting once process was advisable with 60 seconds.After accomplishing melting once, turn over ingot casting and carry out melting again.In order to prevent component segregation, general melt back gets final product for 4 times.
(2), (3) are identical with step (2), (3) of embodiment 2.
Embodiment 6
(1) with purity be not less than 99.9wt% Zr, Al, Cu, Ni component by molar weight than after preparing for 65:7.5:17.5:10; Put into the water jacketed copper crucible of vacuum arc melting furnace; Under the high-purity argon atmosphere protection of melted pure titanium oxygen consumption, utilize electric arc that it is carried out melt back.Fusion current is 200 peaces, and the melting once process was advisable with 60 seconds.After accomplishing melting once, turn over ingot casting and carry out melting again.In order to prevent component segregation, general melt back gets final product for 4 times.
(2), (3) are identical with step (2), (3) of embodiment 3.
Table 3 is that embodiment 4, embodiment 5 and embodiment 6 samples are carried out the three-point bending test, and the fulcrum span is 20 mm, and the pressure head gait of march is 0.64 mm/min.
The result shows, along with the increase of remelting number of times, Zr
65Al
7.5Cu
17.5Ni
10The bending ductility of block amorphous alloy significantly improves.
The present invention is equally applicable to other zirconium-based bulk amorphous alloys, such as Zr
60Al
15Ni
25, Zr
60Cu
30Al
10, Zr
60Cu
20Al
10Pd
10, Zr
50Cu
18Ni
17Al
10Ti
5, Zr
52.5Cu
17.9Ni
14.6Al
10Ti
5, Zr
65Al
7.5Cu
12.5Ni
10Ag
5, or the like, the improvement method and the Zr of their bending ductilities
55Al
10Ni
5Cu
30Block amorphous alloy is identical, this no longer tired stating.
Claims (3)
1. a method of improving the zirconium-based bulk amorphous alloy bending ductility is characterized in that, the concrete steps of this method are following:
The first step; The preparation of original mother alloy ingot: the pure metal that required purity is not less than 99.9wt% by the alloy nominal composition places in the water jacketed copper crucible of vacuum arc melting furnace and melts; Fusion current is 200 peaces; Melting atmosphere is the high-purity argon gas through the molten titanium oxygen consumption, and the melting once time is 60 seconds; After accomplishing melting once, turn over ingot casting and carry out melting again, melt back 4 times, even with the chemical ingredients that guarantees mother alloy ingot;
Second step; The refinement of mother alloy ingot solidified structure: the original mother alloy ingot that the first step is obtained is crushed to a plurality of fritters; The fritter alloy of certain mass is placed in the water jacketed copper crucible again, the melting electric current be 200 peaces with certain electric arc height situation under melt back 3 ~ 6 times;
The 3rd step, the preparation of zirconium-based bulk amorphous alloy: the mother alloy ingot refuse with second step obtained, utilize the absorbing and casting device in the vacuum arc melting furnace, the melt suction water cooled copper mould with mother alloy obtains the high zirconium-based bulk amorphous alloy of bending ductility.
2. according to the described method of improving the zirconium-based bulk amorphous alloy bending ductility of claim 1, it is characterized in that: in the 3rd step, the melting electric current is 100 peaces, and smelting time is 10 seconds, and high-purity argon atmosphere is 1 normal atmosphere.
3. according to the described method of improving the zirconium-based bulk amorphous alloy bending ductility of claim 1, it is characterized in that: the electric arc height described in second step is tungsten electrode and alloy melt surface height, can cover bath surface fully with electric arc and be advisable.
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|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609243A (en) * | 2004-09-16 | 2005-04-27 | 上海交通大学 | Control method of bulk amorphous alloy micro-structure |
| CN101016606A (en) * | 2007-02-08 | 2007-08-15 | 上海交通大学 | Magnesium-base massive non-crystalline material and preparing method thereof |
| CN101538671A (en) * | 2009-04-23 | 2009-09-23 | 上海交通大学 | Rapid solidification superhigh strength magnesium alloy and preparation method thereof |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609243A (en) * | 2004-09-16 | 2005-04-27 | 上海交通大学 | Control method of bulk amorphous alloy micro-structure |
| CN101016606A (en) * | 2007-02-08 | 2007-08-15 | 上海交通大学 | Magnesium-base massive non-crystalline material and preparing method thereof |
| CN101538671A (en) * | 2009-04-23 | 2009-09-23 | 上海交通大学 | Rapid solidification superhigh strength magnesium alloy and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20121003 |