CN101195874A - Method for improving amorphous alloy forming ability - Google Patents
Method for improving amorphous alloy forming ability Download PDFInfo
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- CN101195874A CN101195874A CNA2006101621692A CN200610162169A CN101195874A CN 101195874 A CN101195874 A CN 101195874A CN A2006101621692 A CNA2006101621692 A CN A2006101621692A CN 200610162169 A CN200610162169 A CN 200610162169A CN 101195874 A CN101195874 A CN 101195874A
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Abstract
The invention discloses a preparation method of amorphous alloy, which comprises the following steps: under the gaseous protection, an element is added in one of Zr radical, Ti radical, Mg radical, Cu radical, La radical and Fe radical amorphous alloys, the amorphous alloys are melted in the reaction furnace according to the metric ratio and rapidly cooled to coagulate, and the added element is a lanthanon element. The lanthanon element occupies 0.1 percent to 10 percent of the entire atom percent content of the amorphous alloy. By adopting the method of the invention to prepare amorphous alloy, the requirement to the raw material and the foreign impurity gas content of the reacting container can be reduced, and simultaneously, the amorphous forming capability and performance of the amorphous alloy is enhanced.
Description
Technical field
The present invention relates to a kind of preparation method of non-crystaline amorphous metal.
Background technology
The preparation non-crystaline amorphous metal utilizes the distinctive glass performance of metal: long-range does not have continuous, short range order, and the constant and viscosity of Liquid Structure performance makes its rapid solidification moulding in supercooling liquid phase region near the characteristics of solidifying attitude in the superplasticity district; Compare with crystal alloy, it has high intensity, hardness, wear resistance, solidity to corrosion and high resistance, but also shows characteristics such as good supraconductivity and low magnetic loss, before industries such as IT electronics, machinery, chemical industry are widely used; But; certain density oxygen element is introduced in the impure or not high meeting of purity of raw material of preparation non-crystaline amorphous metal in alloy; simultaneously; a small amount of oxygen element in the shielding gas all can produce very big influence to the formation ability of amorphous; greatly limit the formability of non-crystaline amorphous metal, and then limited the large-scale production of non-crystaline amorphous metal.
At present, produce the non-crystaline amorphous metal of preparation both at home and abroad, in order to eliminate the unfavorable factor of bringing owing to the not high oxygen of introducing of alloying element purity, highly purified metallic substance is selected in the preparation of non-crystaline amorphous metal mostly for use; But, high purity metal because of cost an arm and a leg, production cost is high is not suitable for large-scale production, this just needs us to go to seek a kind of cost-effective method that can improve alloy amorphous formation ability.
Summary of the invention
The objective of the invention is, provide a kind of feasible cost-effective method to solve the above-mentioned defective that causes because of alloying element purity is not high, can increase the amorphous formation ability of alloy to a certain extent by adding the proper amount of rare-earth element, the flexural strength, hardness etc. of alloy are better improved; Reduce production costs thereby reach, make alloy be tending towards the purpose of scale operation.
A kind of preparation method of non-crystaline amorphous metal; be included under the gas shield; a kind of middle element that adds in Zr base, Ti base, Mg base, Cu base, La base and Fe base noncrystal alloy is pressed metering than melting and quick cooled and solidified in Reaktionsofen, the interpolation element is a rare earth element.Be preferably: one or several among Y, Nd, La, Ce, Pr, Sc, Sm, Ho, the Er.
Wherein, also can contain O in described shielding gas or the vacuum environment
2, CO, CO
2, H
2O, SO
2, NO, NO
2And H
2One or more blended foreign gases in the gas, the content of this foreign gas is 1000-10000ppm.
Wherein, shielding gas comprises rare gas element or N
2, SF
6Gas.The purity requirement of shielding gas is that volume percent is greater than 98%.
Wherein, rare earth element accounts for 0.1%～10% of the overall molar content of non-crystaline amorphous metal, is preferably 1%～5%.
Wherein, each raw-material purity in weight percentage is more than or equal to 98%, simultaneously less than 99.5%.
Logical water coolant reaches the purpose of quick cooling melt solution in the reaction vessel, and speed of cooling is 10
6K/s～10
4K/s is preferably 10
5K/s～10
4K/s.
Wherein rare gas element is one or more the mixing in helium, neon, the argon gas.
The preparation method of existing non-crystaline amorphous metal, general requirement foreign gas content is 100ppm; Alloy purity is not subjected to the influence of gas and alloying element purity more than 99.5% during with the assurance alloy casting.
Non-crystaline amorphous metal according to the preparation method of non-crystaline amorphous metal of the present invention preparation has the following advantages: can carry out alloy casting under the not high condition of alloy purity requirement smoothly; protection environmental requirement to non-oxidizing gas simultaneously reduces; the proper amount of rare-earth element is except becoming the layer oxide film in that alloy surface is capable; can also well improve the mechanical property of non-crystaline amorphous metal, help the suitability for industrialized production of block amorphous alloy.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of embodiment 1,2 and Comparative Examples 1 prepared non-crystaline amorphous metal.
Embodiment
The present invention is described further below by embodiment.
Embodiment 1
Present embodiment illustrates the preparation method of lanthanum base noncrystal alloy provided by the invention.
With argon gas (purity 99.99%) is under the prerequisite of shielding gas, and foreign gas content is greater than 1000ppm, the non-crystaline amorphous metal of the following prescription of melting, and the alloy proportion formula is as follows: (La
55Al
20Cu
10Ni
10Co
5)
97(Y, Nd)
3Selected element purity is 99.0%; The concrete experiment condition and the step of smelting amorphous alloy are as follows: 1) adopt the arc-melting furnace melting, the sample forming mould is the water-cooled copper mould, and rate of cooling is 10
4K/s; 2) adopt the stone mill suction nozzle of Φ 3mm, Φ 4mm, Φ 5mm, 2mm * 4mm or 2mm * 5mm as the cast pipeline; 3) according to give into assignment system quality be the alloy sample of 25 grams; 4) adopt the copper mould casting, obtained sample size is: 3mm * 10mm * 100mm; 5) adopt the mode of cast or suction casting to prepare sample.
Embodiment 2
With SF6 (purity 99.99%) is shielding gas, and foreign gas content is greater than 8000ppm, and all elements purity of employing is 98.0%; The composition of non-crystaline amorphous metal is: (Zr
57Al
20Cu
10Ni
8Ti
5)
95(Y, Nd)
5, all the other are with embodiment 1.
Embodiment 3
Present embodiment illustrates the preparation method of cu-based amorphous alloys provided by the invention.
Under argon gas (purity 99.0%) gas shield, foreign gas content is greater than 5000ppm, and selected element purity is 99.2%; The non-crystaline amorphous metal of the following prescription of melting, the alloy proportion formula is: (Cu
45Zr
35Ti
6Ag
14)
90(Ce, Y, Pr)
10, all the other are with embodiment 1.
Embodiment 4
Present embodiment illustrates the preparation method of titanium-based amorphous alloy provided by the invention.
N
2Under the protection of (purity 98.5%), foreign gas content is 9000ppm, the non-crystaline amorphous metal of the following prescription of melting, and alloy proportion is considered as: (Ti
50Ni
15Cu
32Sn
5)
94(Nd, Sc)
6, all the other are with embodiment 1.
Comparative Examples 1
The test performance of the lanthanum base noncrystal alloy for preparing when not adding rare earth element under this Comparative Examples explanation prior art condition; the starting material that adopt are more than 99.9%; with argon gas (purity 99.99%) is shielding gas, and foreign gas content is 100ppm, and other is with embodiment 1.The non-crystaline amorphous metal of preparation is La
55Al
20Cu
10Ni
10Co
5
Comparative Examples 2
The starting material that adopt are more than 99.9%, and the test performance of the lanthanum base noncrystal alloy for preparing when not adding rare earth element, foreign gas content are 100ppm, and other is with embodiment 1.The non-crystaline amorphous metal of preparation is La
55Al
20Cu
10Ni
10Co
5
Comparative Examples 3
The starting material that adopt are more than 99.9%, and not adding rare earth element is the amorphous formation ability of titanium base alloy and the mechanical property of each side, and the non-crystaline amorphous metal of preparation is Ti
50Ni
15Cu
32Sn
5, foreign gas content is 100ppm, other is with embodiment 4.
Test condition:
1) XRD analysis
Whether the XRD powder diffraction analysis is that material is carried out material phase analysis, be amorphous to judge alloy, and this experiment is to carry out on model is the x-ray powder diffraction instrument of D-MAX2200PC.With the copper target emanation, its incident wavelength λ=1.54060
Acceleration voltage is 40KV, and electric current is 20mA, adopts step-scan, and scanning step is 0.04 °.
2) dsc analysis
Mainly be the interval size of gamma transition of observing alloy, inquire into the amorphous formation ability of alloy from another point of view.The instrument of this experiment usefulness is STA4490C, experiment condition: experiment condition: nitrogen is raised to 800 ℃ with the speed of 20K/min.Be used for Δ T between the tested glass zone of transformation.
3) hardness test
The alloy rigidity test sample is taken to the sample and the external sample of melting, and hardness test is to test on the Vickers' hardness experimental machine, and pressure head is 100g or 200g, and the loading time is 10s, and each sample is got three points and got its arithmetical av.
4) three-point bending experiment
Be to carry out span 50mm, loading velocity 0.5mm/min, the flexural strength of test non-crystaline amorphous metal on 1 ton the experimental machine by the GB/T14452-93 standard at the tonnage of newly thinking carefully company.
Test result is as shown in table 1 below:
Table 1
| Flexural strength (MPa) | Hardness (Hv) | The interval Δ T of gamma transition (℃) | Inert protective gas purity (oxygen level ppm) | |
| Embodiment 1 | 567 | 237.7 | 98 | Greater than 1000 |
| Embodiment 2 | 643.9 | 189.1 | 113 | Greater than 8000 |
| Embodiment 3 | 1352.9 | 459.6 | 97 | Greater than 5000 |
| Embodiment 4 | 1891 | 483.5 | 113 | Greater than 9000 |
| Comparative Examples 1 | 520.4 | 217.5 | 65 | 100ppm |
| Comparative Examples 2 | 1287.9 | 422.1 | 39 | 100ppm |
| Comparative Examples 3 | 1821 | 451.9 | 74 | 100ppm |
Wherein, Δ T=Tx-Tg, Tg are glass transition temp, and Tx is a crystallization temperature.Wherein, Tx represents when amorphous alloy is heated to Tx, non-crystalline state will take place change to crystalline state.The process of solid amorphous crystallization has characterized the crystallisation process of supercooled liquid.Δ T is big more, and the amorphous formation ability of expression alloy is strong more.The data variation of the supercooling liquid phase region width Delta T from enforcement power 1,2 and Comparative Examples 1 as can be seen, along with the increase of rare earth element, the supercooling liquid phase region width of alloy has obtained good improvement, amorphous formation ability has improved.
Embodiment 1,2 and Comparative Examples 1 from table 1, embodiment 3 and Comparative Examples 2, embodiment 4 and Comparative Examples 3 can be learnt, mechanical properties such as the intensity of alloy, hardness all obviously improve after adding rare earth element, as seen add a certain amount of rare earth element except changing the not high influence of alloying element purity, can also improve and improve the mechanical property of non-crystaline amorphous metal each side its amorphous formation ability.Simultaneously, embodiments of the invention have adopted purity for more than or equal to 98%, and every performance of the non-crystaline amorphous metal that obtains less than 99.5% starting material is better than Comparative Examples simultaneously, and the Comparative Examples material purity is all greater than 99.5%, further specify the method for the present invention that adopts, raw-material requirement is descended.Simultaneously, the foreign gas content of the reaction vessel of embodiment wants high than Comparative Examples, illustrates that the present invention is low than Comparative Examples for environment requirement.
In addition, by among Fig. 1 as can be seen, add after the rare earth element, the amorphous formation ability of alloy has improved greatly, from the Comparative Examples to embodiment 1, embodiment 2 as seen, the decrystallized ability of alloy has been along with the increase of content of rare earth has strengthened, the Comparative Examples 1 from Fig. 1 as can be seen, alloy has part crystalline state peak when not adding rare earth element; After having added a certain amount of rare earth element, the amorphous formation ability of alloy has improved greatly, and resulting sample is entirely non-crystalline state, shown in embodiment 1, embodiment 2; The degree varies sample that the amorphous formation ability of alloy is improved from the different as can be known rare earth element of embodiment 1,2 simultaneously.
In sum, adopt method of the present invention to prepare non-crystaline amorphous metal, by adding excessive rare earth element, can reduce requirement reduction to the foreign gas content of starting material and reaction vessel, simultaneously the amorphous formation ability of non-crystaline amorphous metal and the performance of non-crystaline amorphous metal are all increased.
Claims (8)
1. the preparation method of a non-crystaline amorphous metal; be included under the gas shield; a kind of middle element that adds in Zr base, Ti base, Mg base, Cu base, La base and Fe base noncrystal alloy is pressed metering than melting and quick cooled and solidified in Reaktionsofen, it is characterized in that: the element of interpolation is a rare earth element.
2. the preparation method of non-crystaline amorphous metal according to claim 1, wherein, described rare earth element comprises one or several among Y, Nd, La, Ce, Pr, Sc, Sm, Ho, the Er.
3. the preparation method of non-crystaline amorphous metal according to claim 1, wherein, described shielding gas comprises rare gas element or N
2, SF
6Gas.
4. the preparation method of non-crystaline amorphous metal according to claim 1, wherein the purity of shielding gas is that volume percent is greater than 98%.
5. according to the preparation method of any described non-crystaline amorphous metal of claim 1, wherein, rare earth element accounts for 0.1%～10% of the overall molar content of non-crystaline amorphous metal.
6. the preparation method of non-crystaline amorphous metal according to claim 1, wherein, rare earth element accounts for the overall mole of non-crystaline amorphous metal percentage, and to optimize content be 1%～5%.
7. according to the preparation method of any described non-crystaline amorphous metal among the claim 1-5, wherein, each raw-material purity in weight percentage is more than or equal to 98%, simultaneously less than 99.5%.
8. the preparation method of non-crystaline amorphous metal according to claim 1 and 2 wherein, also contains O in described shielding gas or the vacuum environment
2, CO, CO
2, H
2O, SO
2, NO, NO
2And H
2One or more blended foreign gases in the gas, the content of this foreign gas is 1000-10000ppm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653849A (en) * | 2011-03-03 | 2012-09-05 | 鸿富锦精密工业（深圳）有限公司 | Zirconium-base amorphous alloy part and manufacturing method thereof |
| CN103334066A (en) * | 2013-06-13 | 2013-10-02 | 上海理工大学 | Cu-Zr-Nd bulk amorphous alloy and preparation method thereof |
| CN106855479A (en) * | 2015-12-08 | 2017-06-16 | 比亚迪股份有限公司 | It is a kind of judgement non-crystaline amorphous metal whether the method for crystallization |
| CN108046402A (en) * | 2017-12-04 | 2018-05-18 | 沈阳大学 | A kind of method using cu-based amorphous alloys degradation pigment wastewater |
| CN108588589A (en) * | 2016-10-21 | 2018-09-28 | 漳州龙文区炼盛合信息技术有限公司 | A kind of amorphous alloy film and preparation method thereof and a kind of high intensity liquid metal handset and preparation method thereof |
-
2006
- 2006-12-07 CN CNA2006101621692A patent/CN101195874A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653849A (en) * | 2011-03-03 | 2012-09-05 | 鸿富锦精密工业（深圳）有限公司 | Zirconium-base amorphous alloy part and manufacturing method thereof |
| US8613812B2 (en) | 2011-03-03 | 2013-12-24 | Hong Fu Jin Precision Industry (Shenzhen) Co., Ltd. | Method of making Zr-rich amorphous alloy article |
| CN103334066A (en) * | 2013-06-13 | 2013-10-02 | 上海理工大学 | Cu-Zr-Nd bulk amorphous alloy and preparation method thereof |
| CN106855479A (en) * | 2015-12-08 | 2017-06-16 | 比亚迪股份有限公司 | It is a kind of judgement non-crystaline amorphous metal whether the method for crystallization |
| CN106855479B (en) * | 2015-12-08 | 2019-07-26 | 比亚迪股份有限公司 | A method of determine amorphous alloy whether crystallization |
| CN108588589A (en) * | 2016-10-21 | 2018-09-28 | 漳州龙文区炼盛合信息技术有限公司 | A kind of amorphous alloy film and preparation method thereof and a kind of high intensity liquid metal handset and preparation method thereof |
| CN108046402A (en) * | 2017-12-04 | 2018-05-18 | 沈阳大学 | A kind of method using cu-based amorphous alloys degradation pigment wastewater |
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Open date: 20080611 |