CN103334066A - Cu-Zr-Nd bulk amorphous alloy and preparation method thereof - Google Patents
Cu-Zr-Nd bulk amorphous alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Cu-Zr-Nd bulk amorphous alloy and a preparation method thereof. The Cu-Zr-Nd bulk amorphous alloy consists of elements Cu, Zr and Nd, wherein the atomic percents of Cu, Zr and Nd are 45-49.5%, 45-49.5% and 1-10% respectively; the diameter is 3-10mm; and the length is 20-60mm. Compared with the Cu-Zr bulk amorphous alloy, the Cu-Zr-Nd bulk amorphous alloy provided by the invention has the advantages that, by adding the rare earth element Nd, great breakthrough is made in the size of the amorphous alloy and the mechanical properties are remarkably improved. The method provided by the invention is characterized by simple process; and the prepared amorphous alloy product has large size, good thermodynamic stability and excellent mechanical properties, and is a bulk amorphous alloy with great application prospect.
Description
Technical field
The present invention relates to a kind of Cu-Zr-Nd bulk amorphous alloys and preparation method thereof.
Background technology
Compare with traditional crystal alloy material, amorphous alloy material has obvious advantages aspect the multinomial use properties, such as: excellent mechanical property, good processing properties, physicalies such as the soft magnetism of good corrosion resistance and excellence, Hard Magnetic.The atomic structure of the uniqueness of non-crystaline amorphous metal has determined its excellent properties, i.e. the short range order of atom, long-range disordered structure.Quench prepares non-crystaline amorphous metal, is that the alloy that will be in molten state is cooled to below the glass transformation temperature fast, and this process do not have crystallization to take place, and then obtains non-crystaline amorphous metal.Required minimum rate of cooling is the critical cooling rate that amorphous becomes in this process, and critical cooling rate is more little, and the amorphous formation ability of corresponding alloy is more strong, and the amorphous critical size of preparing is also more big.It is stronger how to develop amorphous formation ability, and the more stable and more excellent bulk amorphous alloys of mechanical property of thermomechanical property is researchist's problem demanding prompt solution.
The Cu-Zr base large amorphous alloy has strong amorphous formation ability, good thermal stability, excellent mechanical property and cheap cost.Therefore, have huge using value and the market space widely.2004, the Cu-Zr base block amorphous alloy has been obtained breakthrough development, (Chinese Physics Letters, 2004 such as Tang, 21:901) prepare the Cu-Zr binary system block amorphous alloy that diameter is 2mm, but on size and the mechanical property always difficulty breakthrough is arranged.
There are some researches show, increase on the block amorphous alloy size of Cu-Zr base ternary system that for example A.Inoue etc. (Acta mater.2001,49:2645～2652) has prepared the Cu-Zr-Ti non-crystaline amorphous metal of diameter 4mm.
Yet, find in Cu-Zr base ternary system block amorphous alloy through document investigation, added ingredients be mostly Al, Ti etc. (Spcripta Materialia, 2005,53:166) conventional element still finds no the interpolation of rare earth element.China is rare earth big country, and resource is very abundant, and rare earth element has performances such as unique magnetic, electricity, thermodynamics, mechanics, often can improve its many-sided performance by doped with rare-earth elements.Lot of documents report has been arranged, added rare earth element in the non-crystaline amorphous metal outside Cu-Zr base ternary system and can significantly improve its amorphous formation ability, and performances such as magnetic, thermodynamics, mechanics.
But former rare earth element addition means has following shortcoming:
Because rare earth element nd added on Cu-Zr-Ti/Al ternary alloy basis in the past, can not be improved on the size.In addition, the amorphous formation ability of gained alloy, thermal stability and mechanical property are all not high.
Summary of the invention
The present invention carries out in order to address the above problem, purpose is to provide a kind of strong amorphous formation ability that has, the Cu-Zr-Nd bulk amorphous alloys of the mechanical property of good thermostability and excellence, and the preparation method of this Cu-Zr-Nd bulk amorphous alloys.
The Cu-Zr-Nd bulk amorphous alloys that the present invention makes is elementary composition by Cu, Zr and Nd, it is characterized in that: wherein, the atomic percent of Cu is 45%～49.5%, the atomic percent of Zr is 45%～49.5%, the atomic percent of Nd is 1%～10%, the diameter of Cu-Zr-Nd bulk amorphous alloys is 3～10mm, and length is 20～60mm.
The present invention has adopted following method to achieve these goals:
The invention provides a kind of preparation method of Cu-Zr-Nd bulk amorphous alloys, it is characterized in that, may further comprise the steps:
(1) be that 45%～49.5%:45%～49.5%:1%～10% places Cu, Zr and Nd in the arc-melting furnace respectively according to atomic percent;
(2) vacuum tightness with arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element, melt back 4～6 times, and each magnetic agitation 1～3min obtains mother alloy;
(3) mother alloy is placed the suction pouring mould, the heating mother alloy obtains the Cu-Zr-Nd bulk amorphous alloys to molten state after the cooling.
In addition, among the preparation method of above-mentioned Cu-Zr-Nd bulk amorphous alloys, rare gas element is Ar
2, the inert gas pressure in the arc-melting furnace is 800mbar.
In addition, among the preparation method of above-mentioned Cu-Zr-Nd bulk amorphous alloys, when carrying out above-mentioned melting, the arc melting electric current is 200A～250A, and smelting time is 3～5min.
Further, among the preparation method of above-mentioned Cu-Zr-Nd bulk amorphous alloys, when heating, the electric-arc heating electric current is 200A～250A.
Effect and the effect of invention
According to Cu-Zr-Nd bulk amorphous alloys of the present invention, added rare earth element because adopt, so not only the size of non-crystal structure has had very big breakthrough, and mechanical property also improves a lot.
In addition, preparation method's technology of Cu-Zr-Nd bulk amorphous alloys of the present invention is simple, and the combined coefficient height is conducive to industrial applications.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention one.
Fig. 2 is the microhardness of Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention one and the graph of a relation of Nd atom content.
Fig. 3 is the graph of a relation of nano hardness, Young's modulus and the Nd atom content of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention one.
Fig. 4 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention two.
Fig. 5 is the SDC collection of illustrative plates of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention two.
Fig. 6 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention three.
Fig. 7 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention four.
Fig. 8 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention five.
Embodiment
Below in conjunction with accompanying drawing the Cu-Zr-Nd bulk amorphous alloys that the present invention relates to and preparation method thereof is described in detail.Present embodiment is being to implement under the prerequisite with the technical solution of the present invention, and given detailed embodiment and process are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment one
The present invention adds rare earth element nd in Cu-Zr base binary alloy, utilize the copper mold method successfully to make diameter and be 3mm, and length is the Cu-Zr-Nd bulk amorphous alloys of 50mm.This Cu-Zr-Nd bulk amorphous alloys is ternary system, has good thermostability and excellent mechanical property, and its preparation method is as follows:
(1). according to (Cu
50Zr
50)
99Nd
1The chemical ingredients proportioning take by weighing purity respectively greater than 99.99% Cu, Zr and Nd, and place in the arc-melting furnace.This moment, the atomic percent of Cu, Zr and Nd was 49.5:49.5:1.
(2). the vacuum tightness of arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element Ar
2, make air pressure inside reach 800mbar, regulating the arc melting electric current is 200A, melt back 5 times, each melting 4min and while magnetic agitation 1min obtain mother alloy.
(3). mother alloy is placed the suction pouring mould, and regulating the electric-arc heating electric current is 200A, heats this mother alloy to molten state, and namely obtaining diameter after the cooling is 3mm, and length is the cylindrical Cu-Zr-Nd bulk amorphous alloys of 50mm.
In the above-mentioned steps (2), melt back can guarantee that the alloying constituent that produces is more even for 5 times.
Fig. 1 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention one.
As shown in Figure 1, the Cu-Zr-Nd bulk amorphous alloys that obtains is carried out X-ray diffraction analysis (XRD), find that it is not completed into amorphous diffuse peaks completely.
Fig. 2 is the microhardness of Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention one and the graph of a relation of Nd atom content.
Fig. 3 is the graph of a relation of nano hardness, Young's modulus and the Nd atom content of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention one.
Shown in Fig. 2,3, this Cu-Zr-Nd bulk amorphous alloys is carried out Mechanics Performance Testing, its result is as follows: microhardness is 810Hv, and nano hardness is 5.4GPa, and Young's modulus is 68.1Gpa.In contrast to this, the Cu that does not add Nd
50Zr
50The microhardness of alloy is 442Hv, and nano hardness is 4.5GPa, and Young's modulus is 42.2GPa.Above-mentioned experimental result shows that the rare earth element nd of interpolation trace improves a lot to the mechanical property of CuZr alloy.
Embodiment two
The present invention adds rare earth element nd in Cu-Zr base binary alloy, utilize the copper mold method successfully to make diameter and be 3mm, and length is the Cu-Zr-Nd bulk amorphous alloys of 50mm.This Cu-Zr-Nd bulk amorphous alloys is ternary system, has good thermostability and excellent mechanical property, and its preparation method is as follows:
(1). according to (Cu
50Zr
50)
97Nd
3The chemical ingredients proportioning take by weighing purity respectively greater than 99.99% Cu, Zr and Nd, and place in the arc-melting furnace.This moment, the atomic percent of Cu, Zr and Nd was 48.5:48.5:3.
(2). the vacuum tightness of arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element Ar
2, make air pressure inside reach 800mbar, regulating the arc melting electric current is 200A, melt back 6 times, each melting 4min and while magnetic agitation 1min obtain mother alloy.
(3). mother alloy is placed the suction pouring mould, and regulating the electric-arc heating electric current is 250A, heats this mother alloy to molten state, and namely obtaining diameter after the cooling is 3mm, and length is the cylindrical Cu-Zr-Nd bulk amorphous alloys of 50mm.
In the above-mentioned steps (2), melt back can guarantee that the alloying constituent that produces is more even for 6 times.
Fig. 4 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention two.
As shown in Figure 4, the Cu-Zr-Nd bulk amorphous alloys that obtains is carried out X-ray diffraction analysis (XRD), find that it has formed the diffraction peak of disperse, illustrates (Cu
50Zr
50)
97Nd
3Alloy has strong glass forming ability.
Fig. 5 is the SDC collection of illustrative plates of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention two.
As shown in Figure 5, this Cu-Zr-Nd bulk amorphous alloys is carried out heat analysis, to know its glass transformation temperature (T
g), crystallization begins temperature (T
x) and sub-cooled liquid temperature interval (Δ T
x).The DSC collection of illustrative plates of Fig. 5 has significantly shown glass transition and crystallization process, its T
g, T
x, Δ T
xBe respectively 680K, 719K and 39K.
This Cu-Zr-Nd bulk amorphous alloys is carried out Mechanics Performance Testing, its result is as follows: microhardness is 1044Hv, adopting the resulting nano hardness of nano-indenter test is 6.9GPa, and Young's modulus is 108.3GPa, illustrates that this Cu-Zr-Nd bulk amorphous alloys has excellent mechanical property.
Embodiment three
The present invention adds rare earth element nd in Cu-Zr base binary alloy, utilize the copper mold method successfully to make diameter and be 3mm, and length is the Cu-Zr-Nd bulk amorphous alloys of 50mm.This Cu-Zr-Nd bulk amorphous alloys is ternary system, has good thermostability and excellent mechanical property, and its preparation method is as follows:
(1). according to (Cu
50Zr
50)
95Nd
5The chemical ingredients proportioning take by weighing purity respectively greater than 99.99% Cu, Zr and Nd, and place in the arc-melting furnace.This moment, the atomic percent of Cu, Zr and Nd was 47.5:47.5:5.
(2). the vacuum tightness of arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element Ar
2, make air pressure inside reach 800mbar, regulating the arc melting electric current is 230A, melt back 7 times, each melting 4min and while magnetic agitation 1min obtain mother alloy.
(3). mother alloy is placed the suction pouring mould, and regulating the electric-arc heating electric current is 200A, heats this mother alloy to molten state, and namely obtaining diameter after the cooling is 3mm, and length is the cylindrical Cu-Zr-Nd bulk amorphous alloys of 50mm.
In the above-mentioned steps (2), melt back can guarantee that the alloying constituent that produces is more even for 7 times.
Fig. 6 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention three.
As shown in Figure 6, the Cu-Zr-Nd bulk amorphous alloys that obtains is carried out X-ray diffraction analysis (XRD), find not form amorphous diffuse peaks completely.
This Cu-Zr-Nd bulk amorphous alloys is carried out Mechanics Performance Testing, and its result is as follows: microhardness is 830Hv, and adopting the resulting nano hardness of nano-indenter test is 5.9GPa, and Young's modulus is 75.8GPa, and does not add the Cu of Nd
50Zr
50The alloy rigidity test result is 442Hv, and nano hardness is 4.5GPa, and Young's modulus is 42.2GPa, shows that the micro-rare earth element nd of interpolation improves a lot to the mechanical property of CuZr alloy.
Embodiment four
The present invention adds rare earth element nd in Cu-Zr base binary alloy, utilize the copper mold method successfully to make diameter and be 3mm, and length is the Cu-Zr-Nd bulk amorphous alloys of 50mm.This Cu-Zr-Nd bulk amorphous alloys is ternary system, has good thermostability and excellent mechanical property, and its preparation method is as follows:
(1). according to (Cu
50Zr
50)
93Nd
7The chemical ingredients proportioning take by weighing purity respectively greater than 99.99% Cu, Zr and Nd, and place in the arc-melting furnace.This moment, the atomic percent of Cu, Zr and Nd was 46.5:46.5:7.
(2). the vacuum tightness of arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element Ar
2, make air pressure inside reach 800mbar, regulating the arc melting electric current is 200A, melt back 5 times, each melting 4min and while magnetic agitation 1min obtain mother alloy.
(3). mother alloy is placed the suction pouring mould, and regulating the electric-arc heating electric current is 200A, heats this mother alloy to molten state, and namely obtaining diameter after the cooling is 3mm, and length is the cylindrical Cu-Zr-Nd bulk amorphous alloys of 50mm.
In the above-mentioned steps (2), melt back can guarantee that the alloying constituent that produces is more even for 5 times.
Fig. 7 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention three.
As shown in Figure 7, the Cu-Zr-Nd bulk amorphous alloys that obtains is carried out X-ray diffraction analysis (XRD), find not form amorphous diffuse peaks completely.
This Cu-Zr-Nd bulk amorphous alloys is carried out Mechanics Performance Testing, and its result is as follows: microhardness is 875Hv, and adopting the resulting nano hardness of nano-indenter test is 6.3GPa, and Young's modulus is 83.5GPa, and does not add the Cu of Nd
50Zr
50The alloy rigidity test result is 442Hv, and nano hardness is 4.5GPa, and Young's modulus is 42.2GPa, shows that the micro-rare earth element nd of interpolation improves a lot to the mechanical property of CuZr alloy.
Embodiment five
The present invention adds rare earth element nd in Cu-Zr base binary alloy, utilize the copper mold method successfully to make diameter and be 3mm, and length is the Cu-Zr-Nd bulk amorphous alloys of 50mm.This Cu-Zr-Nd bulk amorphous alloys is ternary system, has good thermostability and excellent mechanical property, and its preparation method is as follows:
(1). according to (Cu
50Zr
50)
90Nd
10The chemical ingredients proportioning take by weighing purity respectively greater than 99.99% Cu, Zr and Nd, and place in the arc-melting furnace.This moment, the atomic percent of Cu, Zr and Nd was 45:45:10.
(2). the vacuum tightness of arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element Ar
2, make air pressure inside reach 800mbar, regulating the arc melting electric current is 200A, melt back 5 times, each melting 4min and while magnetic agitation 1min obtain mother alloy.
(3). mother alloy is placed the suction pouring mould, and regulating the electric-arc heating electric current is 200A, heats this mother alloy to molten state, and namely obtaining diameter after the cooling is 3mm, and length is the cylindrical Cu-Zr-Nd bulk amorphous alloys of 50mm.
In the above-mentioned steps (2), melt back can guarantee that the alloying constituent that produces is more even for 5 times.
Fig. 8 is the XRD diffracting spectrum of the Cu-Zr-Nd bulk amorphous alloys of the embodiment of the invention three.
As shown in Figure 8, the Cu-Zr-Nd bulk amorphous alloys that obtains is carried out X-ray diffraction analysis (XRD), find not form amorphous diffuse peaks completely.
This Cu-Zr-Nd bulk amorphous alloys is carried out Mechanics Performance Testing, and its result is as follows: microhardness is 804Hv, and adopting the resulting nano hardness of nano-indenter test is 5.7GPa, and Young's modulus is 65.2GPa, and does not add the Cu of Nd
50Zr
50The alloy rigidity test result is 442Hv, and nano hardness is 4.5GPa, and Young's modulus is 42.2GPa, shows that the micro-rare earth element nd of interpolation improves a lot to the mechanical property of CuZr alloy.
Utilizability on the industry
The present invention is by control high vacuum copper mold processing parameter and regulate chemical ingredients, directly on Cu-Zr binary alloy basis, directly add rare earth Nd, thereby prepare strong amorphous formation ability, good thermostability and the bulk amorphous alloys of excellent mechanical property.The Cu-Zr-Nd bulk amorphous alloys that is prepared from by the inventive method has strong amorphous formation ability, good thermostability and excellent mechanical property, bigger breakthrough is also arranged on the size, at the high performance structures material, sports goods, fields such as miniature accurate device can access widely and use.
Claims (5)
1. a Cu-Zr-Nd bulk amorphous alloys is elementary composition by Cu, Zr and Nd, it is characterized in that:
Wherein, the atomic percent of Cu is that the atomic percent of 45%～49.5%, Zr is that the atomic percent of 45%～49.5%, Nd is 1%～10%,
The diameter of described Cu-Zr-Nd bulk amorphous alloys is 3～10mm, and length is 20～60mm.
2. the preparation method of a Cu-Zr-Nd bulk amorphous alloys is characterized in that, may further comprise the steps:
(1). be that 45%～49.5%:45%～49.5%:1%～10% places Cu, Zr and Nd in the arc-melting furnace respectively according to atomic percent;
(2). the vacuum tightness of described arc-melting furnace is adjusted to 5.5 * 10
-5Mbar charges into rare gas element, melt back 4～6 times, and each magnetic agitation 1～3min obtains mother alloy;
(3). described mother alloy is placed the suction pouring mould, heat described mother alloy to molten state, obtain described Cu-Zr-Nd bulk amorphous alloys after the cooling.
3. the preparation method of Cu-Zr-Nd bulk amorphous alloys according to claim 2 is characterized in that:
Wherein, described rare gas element is Ar
2, the described inert gas pressure in the described arc-melting furnace is 800mbar.
4. the preparation method of Cu-Zr-Nd bulk amorphous alloys according to claim 2 is characterized in that:
Wherein, when carrying out described melting, the arc melting electric current is 200A～250A, and smelting time is 3～5min.
5. the preparation method of Cu-Zr-Nd bulk amorphous alloys according to claim 2 is characterized in that:
Wherein, when carrying out described heating, the electric-arc heating electric current is 200A～250A.
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|---|---|---|---|---|
| CN1556239A (en) * | 2004-01-12 | 2004-12-22 | 大连理工大学 | Cu-Zr-Nb series block non crystalline alloy |
| CN1948543A (en) * | 2006-11-03 | 2007-04-18 | 北京航空航天大学 | Copper base large non crystal alloy and its preparation method |
| CN1958831A (en) * | 2005-11-01 | 2007-05-09 | 中国科学院物理研究所 | Copper-zirconium based amorphous alloy, and preparation method |
| CN101195874A (en) * | 2006-12-07 | 2008-06-11 | 比亚迪股份有限公司 | Method for improving amorphous alloy forming ability |
| CN102912261A (en) * | 2012-10-23 | 2013-02-06 | 上海交通大学 | Zirconium-based amorphous alloy and preparation method thereof |
-
2013
- 2013-06-13 CN CN2013102320739A patent/CN103334066A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556239A (en) * | 2004-01-12 | 2004-12-22 | 大连理工大学 | Cu-Zr-Nb series block non crystalline alloy |
| CN1958831A (en) * | 2005-11-01 | 2007-05-09 | 中国科学院物理研究所 | Copper-zirconium based amorphous alloy, and preparation method |
| CN1948543A (en) * | 2006-11-03 | 2007-04-18 | 北京航空航天大学 | Copper base large non crystal alloy and its preparation method |
| CN101195874A (en) * | 2006-12-07 | 2008-06-11 | 比亚迪股份有限公司 | Method for improving amorphous alloy forming ability |
| CN102912261A (en) * | 2012-10-23 | 2013-02-06 | 上海交通大学 | Zirconium-based amorphous alloy and preparation method thereof |
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Application publication date: 20131002 |