CN101347830A - Method for improving massive amorphous alloy plasticity by controlling solidification condition - Google Patents
Method for improving massive amorphous alloy plasticity by controlling solidification condition Download PDFInfo
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- CN101347830A CN101347830A CNA2007100121627A CN200710012162A CN101347830A CN 101347830 A CN101347830 A CN 101347830A CN A2007100121627 A CNA2007100121627 A CN A2007100121627A CN 200710012162 A CN200710012162 A CN 200710012162A CN 101347830 A CN101347830 A CN 101347830A
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- amorphous alloy
- bulk amorphous
- plasticity
- alloy
- temperature
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007711 solidification Methods 0.000 title 1
- 230000008023 solidification Effects 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910015365 Au—Si Inorganic materials 0.000 description 1
- -1 La system Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
the invention relates to a technology for manufacturing bulk amorphous alloy, in particular to a method for improving the plasticity of the bulk amorphous alloy by controlling the concretion condition. The method is low in the technological cost and is convenient and simple to be applied, the plasticity performance of the bulk amorphous alloy can be improved obviously and the method is suitable for most amorphous systems. The invention adopts a copper mould casting method: by adjusting the casting temperature, the temperature of a alloy fused mass is ensured between the liquidus temperature and the temperature that the liquidus temperature is added with 500k, then the casting is carried out, nano-crystals that are evenly distributed within the range of 1-15nm are obtained from the samples, thereby leading that the bulk amorphous alloy has high plasticity. The invention develops a novel method for improving the plasticity of the bulk amorphous alloy and broadens the application field of the bulk amorphous alloy.
Description
Technical field
The present invention relates to the technology of bulk amorphous alloy preparation, be specially a kind of method of improving the plasticity of bulk amorphous alloy by the control curing condition.
Background technology
People such as nineteen sixty U.S. professor Duwez adopt the melt supercooled method at first to make Au-Si series non-crystalline state alloy, over surplus in the of 40 year, all kinds of amorphous soft magnetic alloys that with Fe system, Ni system, Co are representative have than the commercial crystal alloy of routine excellent magnetism energy more in many aspects because of it, use in technology such as electric power, electronics, information.But the noncrystalline state of the non-crystaline amorphous metal of this quasi-tradition need surpass 10
6The high critical cooling rate of K/s could form, and finished product mostly is low-dimensional shapes such as film, band, filament or powder, and its thickness or diameter generally all are no more than 50 μ m, and this has just limited them in actual application in engineering scope greatly.Since 1988, be that the seminar of representative takes the lead in developing the block amorphous alloys such as La system, Mg system, Zr system, Pd system, Ti system, Fe system, Cu system that three-dimensional dimension all reaches the 1mm magnitude with Japanese Inoue professor and U.S. professor Johnson.The block amorphous alloy of multicomponent has extremely strong amorphous (glass) formation ability (GFA), and its critical cooling rate is more much lower than traditional non-crystaline amorphous metal, generally all is no more than 10
3The K/s magnitude.
Because the particularity of its structure, block amorphous alloy is compared with the crystal alloy of identical composition, have plurality of advantages such as lower elastic modelling quantity, high elastic limit (2.0%), high yield strength, high fracture toughness and excellent corrosion resistant performance, it is used as structural material have great prospect.But bulk amorphous alloy destroys with shear pattern usually, does not have macroscopical plasticity, has limited its practical application as structural material.
In addition, find different its performance differences of this scantling simultaneously, the amorphous performance of identical component Different Preparation preparation is variant, and its performance of amorphous of the same alloy composition of different people preparation is also variant, and the performance of the different local materials of same sample is variant.This unstable properties also is the big resistance that material is used.
In recent years, people are finding to have made extensive work on the plasticity blocky metal-glass, find to have bulk amorphous alloy or its composite of tangible macroscopical compression plasticity at present on Zr, Cu, Ti base alloy.Still there are dispute in method therefor or means or do not have generality.Therefore, a kind of significant and use value of the method for improving bulk amorphous alloy plasticity of development with certain universality.
Summary of the invention
The object of the present invention is to provide and a kind ofly improve the method for bulk amorphous alloy plasticity by the control curing condition, this method technology cost is low and simple and easy to do, can obviously improve the plastic property of bulk amorphous alloy.
Technical scheme of the present invention is:
A kind of method of improving bulk amorphous alloy plasticity by the control curing condition, adopt copper mold to cast and prepare the bulk amorphous alloy sample, what curing condition was separated out on the bulk amorphous alloy matrix evenly by controlling, disperse distributes is nanocrystalline, wherein nanocrystalline yardstick is 1～15nm, volume fraction is 1～15%, thereby in the bearing load process, bring out the formation of multiple shear bands, improve the plasticity of bulk amorphous alloy.Its concrete technological parameter is as follows: vacuum 10
-2～10
-4Pa, cast temperature adds 500K (being preferably the above 100-300K of liquidus temperature), cooling velocity 10～10 at liquidus temperature to the liquidus temperature of alloy
2K/s.
Prepared bulk amorphous alloy mechanical performance index is as follows:
Compression plastic strain ε
p=2%～40%.
The metal bath that the present invention can form amorphous bulk has the tendency of strong formation local order structure, and this local order structure can fade away along with the rising of temperature.According to non-classical forming core theory, in process of setting, these local order's structures can be left over or serve as the core of heterogeneous forming core and be grown up.This method is by the control cast temperature, thereby amorphous sample had on a kind of noncrystal substrate evenly, disperse is distributing the nanocrystalline microstructure of yardstick in 1～15nm scope.This microstructure is easily brought out the formation of multiple shear bands and is made sample have macroscopical plasticity under the room temperature.
The method base reason of improving bulk amorphous alloy plasticity provided by the invention is: by the control cast temperature, amorphous sample is had on a kind of noncrystal substrate evenly, disperse is distributing the nanocrystalline microstructure of yardstick in 1～15nm scope.Nanocrystalline and the matrix on every side of separating out has good binding, in the time spent of doing of plus load, and conduction stress that can be good, but because both differences on elastic performance, it is concentrated relatively to be easy to generate stress, thereby germinates a large amount of shear bands.In the expansion process of shear band, between shear band and shear band, shear band and nanocrystalline the interaction of separating out make its propagation direction generation deviation, bifurcated or germinate a large amount of secondaries, three shear bands, thereby strain is distributed on the whole sample, the plasticity of sample is significantly improved.
The advantage that the present invention has:
1, the present invention has adopted the copper mold casting technique by the control cast temperature, and cost is low and simple and easy to do.
2, the present invention can be suitable for most of bulk amorphous alloy systems, as Cu, Zr, Ti base etc., by this method sample is obtained on a kind of noncrystal substrate evenly, disperse is distributing the nanocrystalline microstructure of yardstick in 1～15nm scope, thereby improve the plasticity of bulk amorphous alloy, further promoted the application of bulk amorphous alloy.
Description of drawings
Fig. 1 a-b is that (Fig. 1 a) and DSC curve (Fig. 1 b) for the X-alpha spectrum of the sample that obtains under the different pouring temperature.
Fig. 2 a-d is the high-resolution photo of the sample that obtains under the different pouring temperature.
Fig. 3 is the compression stress strain curve of the sample that obtains under the different pouring temperature.
The specific embodiment
The present invention is described in detail in detail by the following examples.
Embodiment 1
The alloy of selecting is Cu-Zr-Al, and concrete composition is: 47.5%Cu, 47.5%Zr, 5%Al (atomic percent).
The smelting process of Cu-Zr-Al foundry alloy of the present invention is a routine techniques, the present embodiment foundry alloy smelt concrete technological parameter and process as follows: the used raw material of present embodiment are respectively Zr, Cu, Al high pure metal (purity is not less than 99.9wt.%); Master alloy ingot adopts electric arc melting, at first working chamber is evacuated to 10
-3～10
-4Pa, and then feeding high-purity argon gas (purity is 99.99wt.%) carries out melting; Before the molten alloy,, form the dividing potential drop of titanium oxide with oxygen in the further reduction working chamber by oxidation reaction at first with the fusing of Ti ingot; Even as far as possible for the composition that guarantees alloy cast ingot, each alloy cast ingot all needs to turn refining 3～5 times; Alloy cast ingot is crushed to fritter, has aperture below the fritter alloy of certain mass is put into and (behind the quartz ampoule of diameter 1～1.5mm), working chamber is evacuated to 10
-3～10
-4Pa carries out induction melting again.Control the alloy melt temperature, the copper mold under with high-purity argon gas the alloy melt in the quartz ampoule being sprayed into, obtaining diameter is the sample of 2mm, cooling velocity 10～10
2K/s.The temperature of alloy melt is divided into two scopes: liquidus temperature to liquidus temperature adds 500K and liquidus temperature adds two stages more than the 500K, and below narration is distinguished with low temperature and high temperature respectively.Analyze low temperature and high temperature structures of samples with X ray, differential scanning calorimetric analysis and high resolution electron microscopy, high temperature sample (the alloy melt actual temp is 1973K) is pure non crystalline structure as can be known, and the structure of low temperature sample (the alloy melt actual temp is 1273K) is that disperse is uniform-distribution with nanocrystalline on the noncrystal substrate, yardstick is 1～15nm, and percent by volume is about 8%.The room temperature compression test shows, the pure amorphous sample (high temperature sample) that obtains shows the brittle fracture feature of typical bulk amorphous alloy, compression plastic strain is about 0.1%, and the low temperature sample shows good plastic deformation ability, and compression plastic strain is about 12.5%.
Fig. 1 a-b is the X-alpha spectrum and the DSC curve of the Cu-Zr-Al alloy of low temperature and high temperature cast.By analysis as can be known, the X-alpha spectrum of two samples and DSC curve all have typical non crystalline structure feature.
Fig. 2 a-d is the high-resolution photo of the Cu-Zr-Al alloy of low temperature and high temperature cast.By Fig. 2 a-d as can be known, high temperature sample (Fig. 2 a-b) is typical pure amorphous, and low temperature sample (Fig. 2 c-d) contains a large amount of nanocrystalline.
Fig. 3 is the compression stress and the strain curve of the Cu-Zr-Al alloy of low temperature and high temperature cast.
Because the low temperature sample contains a large amount of nanocrystalline, improved the plastic property of bulk amorphous alloy greatly, bring up to 12.5% by 0.1% of pure amorphous.
Difference from Example 1 is:
Alloying component is 62%Zr, 15.4%Cu, 12.6%Ni, 10%Al (atomic percent).The copper mold concrete technological parameter of casting is as follows: vacuum 10
-3～10
-4Pa, cooling velocity 10～10
2K/s.The nanocrystalline percent by volume that the low temperature sample contains is about 3～5%.The plastic strain of high temperature sample (the alloy melt actual temp is 1873K) is about 0.5%, and the plastic strain of low temperature sample (the alloy melt actual temp is 1273K) is 12.0%.
Embodiment 3
Difference from Example 1 is:
Alloying component is 55%Zr, 5%Ni, 10%Al, 30%Cu (atomic percent).The copper mold concrete technological parameter of casting is as follows: vacuum 10
-3～10
-4Pa, cooling velocity 10～10
2K/s.The nanocrystalline percent by volume that the low temperature sample contains is about 1～2%.The plastic strain of high temperature sample (the alloy melt actual temp is 1973K) is about 0.1%, and the plastic strain of low temperature sample (the alloy melt actual temp is 1273K) is 3.5%.
Table 1 is the mechanical property of the sample that obtains under the different pouring temperature
In the table 1, high temperature is that liquidus temperature adds the above temperature of 500K; Low temperature is the temperature that liquidus temperature to liquidus temperature adds 500K.
Claims (3)
1, a kind of method of improving bulk amorphous alloy plasticity by the control curing condition, it is characterized in that: utilize the copper mold casting, what curing condition was separated out on the bulk amorphous alloy matrix evenly by controlling, disperse distributes is nanocrystalline, wherein nanocrystalline yardstick is 1～15nm, and volume fraction is 1～15%; When adopting copper mold casting preparation bulk amorphous alloy sample, the temperature of its alloy melt is that liquidus temperature to liquidus temperature adds between the 500K.
2, according to the described method of improving the plasticity of bulk amorphous alloy of claim 1, it is characterized in that: the copper mold concrete technological parameter of casting is as follows: vacuum 10
-2～10
-4Pa, cooling velocity 10～10
2K/s.
3, according to the described method of improving the plasticity of bulk amorphous alloy of claim 1, it is characterized in that: prepared bulk amorphous alloy mechanical performance index is as follows: compression plastic strain ε
p=2%～40%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100121627A CN101347830A (en) | 2007-07-18 | 2007-07-18 | Method for improving massive amorphous alloy plasticity by controlling solidification condition |
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|---|---|---|---|
| CNA2007100121627A CN101347830A (en) | 2007-07-18 | 2007-07-18 | Method for improving massive amorphous alloy plasticity by controlling solidification condition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967552A (en) * | 2010-10-11 | 2011-02-09 | 清华大学 | Post-processing method for improving plasticity of amorphous alloy by using cyclic load |
| CN102021501B (en) * | 2009-09-16 | 2012-07-04 | 中国科学院金属研究所 | Method for improving forming ability and strength of amorphous alloy by controlling solidifying condition |
| CN103757631A (en) * | 2014-01-27 | 2014-04-30 | 沈阳大学 | Preparation method of high-entropy AlCoNiCrFeMo alloy coating |
| CN103757514A (en) * | 2014-01-27 | 2014-04-30 | 沈阳大学 | High-entropy AlCoCrFeNiCuC alloy and preparation method thereof |
-
2007
- 2007-07-18 CN CNA2007100121627A patent/CN101347830A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021501B (en) * | 2009-09-16 | 2012-07-04 | 中国科学院金属研究所 | Method for improving forming ability and strength of amorphous alloy by controlling solidifying condition |
| CN101967552A (en) * | 2010-10-11 | 2011-02-09 | 清华大学 | Post-processing method for improving plasticity of amorphous alloy by using cyclic load |
| CN101967552B (en) * | 2010-10-11 | 2012-06-20 | 清华大学 | Post-processing method for improving plasticity of amorphous alloy by using cyclic load |
| CN103757631A (en) * | 2014-01-27 | 2014-04-30 | 沈阳大学 | Preparation method of high-entropy AlCoNiCrFeMo alloy coating |
| CN103757514A (en) * | 2014-01-27 | 2014-04-30 | 沈阳大学 | High-entropy AlCoCrFeNiCuC alloy and preparation method thereof |
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Open date: 20090121 |