CN102108474A - Zirconium-based amorphous alloy and preparation method thereof - Google Patents

Zirconium-based amorphous alloy and preparation method thereof Download PDF

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CN102108474A
CN102108474A CN2009102543976A CN200910254397A CN102108474A CN 102108474 A CN102108474 A CN 102108474A CN 2009102543976 A CN2009102543976 A CN 2009102543976A CN 200910254397 A CN200910254397 A CN 200910254397A CN 102108474 A CN102108474 A CN 102108474A
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zirconium
amorphous alloy
base amorphous
vacuum tightness
working chamber
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CN102108474B (en
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宫清
李运春
菅永喜
张法亮
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BYD Co Ltd
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Priority to PCT/CN2010/078525 priority patent/WO2011057552A1/en
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Abstract

The invention provides zirconium-based amorphous alloy. The general formula of the zirconium-based amorphous alloy is as follow: (ZraMbNc)100-xQx, wherein M is at least a transition metal except zirconium; N is Be or Al; Q is at least one of CaO, MgO, Y2O3 and Nd2O3; a, b and c represent atomic percent; a is not less than 45 and is not more than 75; b is not less than 20 and is not more than 40; c is not less than 1 and is not more than 25; the sum of a, b and c is 100; and x is not less than 1 and is not more than 15. The invention also provides a preparation method of the zirconium-based amorphous alloy. The method comprises the following steps: mixing Zr, M, N and Q according to the mole ratio of ZraMbNc to Q to Zr and then carrying out melting, filtering, pouring and cooling in sequence, wherein the mole ratio of ZraMbNc to Q to Zr is 100-x:x+y:y; and x is not less than 1 and is not more than 15 and y is not less than 0.1 and is not more than 5. The zirconium-based amorphous alloy has high bending strength and maximum plastic strain and impact toughness, thus having good toughness.

Description

A kind of zirconium-base amorphous alloy and preparation method thereof
Technical field
The present invention relates to the preparation method of a kind of zirconium-base amorphous alloy and this zirconium-base amorphous alloy.
Background technology
Amorphous alloy material is owing to have the unordered and special construction of short range order of long-range, thereby has a high strength, high rigidity, wear resistance, solidity to corrosion, superior performances such as bigger elastic limit and high resistance, but also show characteristics (W.L.Johnson such as good supraconductivity and low magnetic loss, Bulk-FormingMetallic Alloys:Science and Technology, MRS BULLETIN, in October, 1999, the 42-56 page or leaf), therefore amorphous alloy material is considered to the new structural material of potentialization, thereby is widely applied to machinery, medical treatment, the IT electronics, fields such as military project.
Need highly purified raw material and very high vacuum tightness environment in the non-crystaline amorphous metal preparation process of routine, a spot of oxygen or other impurity all will greatly reduce the amorphous formation ability of alloy.Yet so harsh production process has increased the production cost of non-crystaline amorphous metal goods greatly, has limited the widespread use of non-crystaline amorphous metal.
And, some shortcomings of non-crystaline amorphous metal self have also limited its application, concrete, amorphous alloy material is owing to self structure is special, in carry load, can produce various deformation mechanisms and come resistance to deformation unlike crystalline material inside, therefore when stress reaches breaking tenacity unexpected fracture can take place, cause the generation of disaster accident, thereby restricted the application of amorphous alloy material in the structured material field.
Disclose a kind of bulk-solidifying amorphous among the CN1578846A, this alloy comprises: a kind of matrix bulk-solidifying amorphous and additional metal of alloying that comprises multiple metal ingredient, its general formula is as (M 1aM 2bM 3c) 100-xQ x, wherein, Q is additional metal of alloying, and concrete La, Y, Ca, Al and the Be of being selected from.In this patent application, though on the basis of zirconium-base amorphous alloy, can suppress the deleterious effects of impurity in the amorphous production process such as oxygen by adding oxytropism elements such as La, Y, Ca, Al and Be, thereby reduction working condition, and then reduce production costs, yet, the toughness of this zirconium-base amorphous alloy still do not have be improved significantly.
Summary of the invention
An object of the present invention is provides a kind of good flexible zirconium-base amorphous alloy that has in order to overcome the relatively poor defective of existing zirconium-base amorphous alloy toughness.
Another object of the present invention provides the preparation method of this zirconium-base amorphous alloy.
The invention provides a kind of zirconium-base amorphous alloy, the general formula of this zirconium-base amorphous alloy is as (Zr aM bN c) 100-xQ x, wherein, M is at least a transition metal except that zirconium, and N is Be or Al, and Q is CaO, MgO, Y 2O 3, Nd 2O 3In at least a, a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, a+b+c=100,1≤x≤15.
The present invention also provides a kind of preparation method of zirconium-base amorphous alloy, and this method comprises Zr, M, N and Q according to Zr aM bN c: the mol ratio of Q: Zr is the mixed of 100-x: x+y: y, carry out fusion, filtration, cast and cooling then successively, thereby the general formula of the zirconium-base amorphous alloy that makes is as (Zr aM bN c) 100-xQ x, wherein, M is at least a transition metal except that zirconium, and N is Be or Al, and Q is CaO, MgO, Y 2O 3, Nd 2O 3In at least a, a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, a+b+c=100,1≤x≤15,0.1≤y≤5.
By discovering, in zirconium-base amorphous alloy, contain ZrO usually 2, ZrO 2From the high temperature four directions to low temperature the transition process of oblique side's phase, volumetric expansion 5-7%, in the rapid process of cooling that forms amorphous, the alloy exterior cooling is solidified, and inner cooling is slow relatively, in inner crystal transition process, there are not enough expansion spaces and the expansion stress that produces may be the one of the main reasons that causes alloy embrittlement.The present inventor is surprised to find that, by adopting the preparation method of described zirconium-base amorphous alloy provided by the invention, introduces metal oxide (as CaO, MgO, Y in zirconium-base amorphous alloy on the one hand 2O 3, Nd 2O 3In at least a), thereby can significantly improve the toughness of described zirconium-base amorphous alloy; On the other hand, in the system of preparation zirconium-base amorphous alloy, add excessive Zr and metal oxide (as CaO, MgO, Y 2O 3, Nd 2O 3In at least a), described excessive metal oxide and ZrO 2React and generate the infusible composite oxides, described excessive Zr replenishes ZrO simultaneously 2The Zr atom of reaction back loss, thus ZrO in the zirconium-base amorphous alloy that finally makes can significantly be reduced 2Content, and then avoided ZrO 2Structure in temperature-fall period owing to crystal conversion produces expansion stress.Therefore, adopt the prepared zirconium-base amorphous alloy of described zirconium-base amorphous preparation method provided by the invention to eliminate, thereby have good toughness owing to alloy embrittlement reduces the flexible defective.
Learn that according to the experiment detection bending strength of described zirconium-base amorphous alloy provided by the invention is up to 2780MPa, maximum plastic strain is up to 4.5%, and impelling strength is up to 110KJ/m 2, therefore have good toughness.
Description of drawings
Fig. 1 represents the stress-strain curve according to embodiment 1-4 and the prepared zirconium-base amorphous alloy of Comparative Examples 1-2;
Fig. 2 represents the XRD diffracting spectrum according to embodiment 1 and 2 prepared zirconium-base amorphous alloys.
Embodiment
The general formula of described zirconium-base amorphous alloy provided by the invention is as (Zr aM bN c) 100-xQ x, wherein, M is at least a transition metal except that zirconium, and N is Be or Al, and Q is CaO, MgO, Y 2O 3, Nd 2O 3In at least a, a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, a+b+c=100,1≤x≤15.In order to make described zirconium-base amorphous alloy obtain better toughness, in the above-mentioned general formula of described zirconium-base amorphous alloy, the span of a, b, c, x preferably as: 50≤a≤70,25≤b≤35,3≤c≤23,2≤x≤5.
In a kind of preferred implementation, in the general formula of described zirconium-base amorphous alloy, M is at least two kinds among Ti, Ni, the Cu, and under this preferable case, described zirconium-base amorphous alloy not only has better toughness, and has bigger amorphous formation ability.Under the most preferred situation, M is Ni and Cu, perhaps is Ti, Ni and Cu.At M is under the situation of Ni and Cu, and in described zirconium-base amorphous alloy, the atomic ratio of Ni and Cu can be 1: 3.5-10; At described M is under the situation of Ti, Ni and Cu, and the atomic ratio of Ni, Cu and Ti can be 1: 1-2: 1.2-2.5.
The present invention also provides a kind of preparation method of zirconium-base amorphous alloy, and this method comprises Zr, M, N and Q according to Zr aM bN c: the mol ratio of Q: Zr is the mixed of 100-x: x+y: y, carry out fusion, filtration, cast and cooling then successively, thereby the general formula of the zirconium-base amorphous alloy that makes is as (Zr aM bN c) 100-xQ x, wherein, M is at least a transition metal except that zirconium, and N is Be or Al, and Q is CaO, MgO, Y 2O 3, Nd 2O 3In at least a, a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, a+b+c=100,1≤x≤15,0.1≤y≤5.
In described method provided by the invention, the add-on of Zr and Q makes Zr aM bN c: the mol ratio of Q: Zr is 100-x: x+y: y, on the one hand, adds the Q of x molar ratio in described compound, thereby introduce Q (metal oxide such as CaO, MgO, Y in described zirconium-base amorphous alloy 2O 3, Nd 2O 3In at least a); On the other hand, the extra Q (promptly excessive relatively Q) that adds the y molar ratio in described compound, the ZrO that produces in the Q of y molar ratio and the described zirconium-base amorphous alloy forming process 2Reacting forms the infusible composite oxides, and separates from described zirconium-base amorphous alloy by follow-up filtration step, and the Zr of the y molar ratio of described extra adding simultaneously replenishes ZrO 2Participate in the Zr atom of reaction back loss.In the present invention, the span of y can be according to common preparation general formula such as Zr aM bN c(wherein, M is at least a transition metal, and N is Be or Al, and a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, the ZrO that produces in the process of zirconium-base amorphous alloy a+b+c=100) 2Molar weight and determine.The ZrO that produces in the preparation process of described zirconium-base amorphous alloy 2Molar weight can obtain by the oxygen level of measuring in the zirconium-base amorphous alloy that finally makes, described oxygen level can adopt IRO-II oxygen analysis instrument to test and obtain.Usually, at Zr aM bN c: the mol ratio of Q: Zr is 100-x: x+y: y, and under the situation of 1≤x≤15, the span of y can for more than or equal to and smaller or equal to 5, be preferably 0.2≤y≤2.
In order to make the zirconium-base amorphous alloy that finally makes have better toughness, preferably make in the general formula of the zirconium-base amorphous alloy that finally makes, the span of a, b, c, x is as 50≤a≤70,25≤b≤35,3≤c≤23,2≤x≤5.
In a kind of preferred implementation, in the general formula of described zirconium-base amorphous alloy, M is at least two kinds among Ti, Ni, the Cu, and under this preferable case, described zirconium-base amorphous alloy not only has better toughness, and has bigger amorphous formation ability.Under the most preferred situation, M is Ni and Cu, perhaps is Ti, Ni and Cu.At M is under the situation of Ni and Cu, and in described zirconium-base amorphous alloy, the atomic ratio of Ni and Cu can be 1: 3.5-10; At described M is under the situation of Ti, Ni and Cu, and the atomic ratio of Ni, Cu and Ti can be 1: 1-2: 1.2-2.5.
Described being melted in the smelting furnace with working chamber carried out, described fused method is included under the above temperature more than 100 ℃ of fusing point of described zirconium-base amorphous alloy, it is 0.1-10Pa that described working chamber is evacuated to vacuum tightness, and charging into rare gas element to vacuum tightness then is 30-50kPa.
In described method provided by the invention, described being melted in the smelting furnace with working chamber carried out, there is no particular limitation for described fused method, under the preferable case, described fused method is included under the above temperature more than 100 ℃ of fusing point of described zirconium-base amorphous alloy, it is 0.1-10Pa that described working chamber is evacuated to vacuum tightness, and charging into rare gas element to vacuum tightness then is 30-50kPa.Further under the preferable case, under the above 100-300 of fusing point that described fused method is included in described zirconium-base amorphous alloy ℃ the temperature, it is 0.5-5Pa that described working chamber is evacuated to vacuum tightness, and charging into rare gas element to vacuum tightness then is 35-45kPa.Described rare gas element can be in neutral element gas such as helium, neon, argon gas, krypton gas, xenon, the radon gas at least a, be preferably helium and/or argon gas.In the present invention, described vacuum tightness is meant absolute pressure.
Described mixture carries out under above-mentioned melting condition after the melting, and the melt that obtains after the described fusion was left standstill 1-5 minute, makes described melt filtration then, and pours into a mould.Described leaving standstill on the one hand can make the temperature of described melt reduce to suitable teeming temperature; Also help the slag that makes in the described melt on the other hand and from liquid, be suspended to the surface, thereby guarantee that described slag can fully filter out.
In described method provided by the invention, described filtering method can be for making the melt that obtains after the described fusion through high temperature resistant net, and the mesh diameter of described high temperature resistant net can be the 0.5-5 millimeter, is preferably the 0.8-2 millimeter.Described high temperature resistant net can be served as reasons and can be born the filter screen that the 750-1500 ℃ of various materials of pyritous are made, and described high temperature resistant net for example can be woven wire, ceramic network, molybdenum filament net or fibrous reticulum.
Described cast can be carried out in the mould of routine, and there is no particular limitation in the present invention for the condition of described cast, for example can comprise: temperature is the above 30-80 of the fusing point of described zirconium-base amorphous alloy ℃, protection of inert gas.Described rare gas element can be in neutral element gas such as helium, neon, argon gas, krypton gas, xenon, the radon gas at least a, be preferably helium and/or argon gas.
Process of cooling after the described cast can be implemented in the presence of the shielding gas of various routines; described shielding gas is selected at least a in neutral element gas such as helium, neon, argon gas, krypton gas, xenon, the radon gas usually, is preferably helium and/or argon gas.
The present invention is further detailed explanation by the following examples.
Embodiment 1
Present embodiment is used to illustrate described zirconium-base amorphous alloy provided by the invention and preparation method thereof.
According to Zr 55Al 10Cu 30Ni 5: Y 2O 3: the mol ratio of Zr is about 97: 4: thus 1 ratio feeds intake to mix and obtains mixture, wherein, Al, Cu and Ni add with the form of high pure metal, and Zr adds Y with the form of zirconium sponge (available from Baotai Huashen Titanium Industry Co., Ltd.) 2O 3Form with oxide compound adds.It is that 25 kilograms intermediate frequency vacuum induction melting furnace (is produced by Sante Vacuum Metallurgical Tech Ind Co., Ltd., Jinzhou City that the mixture that obtains is added to rated capacity, model is ZG-03) the working chamber in, it is 3Pa that described working chamber is evacuated to vacuum tightness, charge into argon gas then, and the vacuum tightness of controlling described working chamber is 40kPa.The melting under the power of 25kW of described mixture is melted to whole, (more than the fusing point at described zirconium-base amorphous alloy 100 ℃) insulation under 950 ℃ 5 minutes, left standstill then 3 minutes, treat that temperature drops to 920 ℃ (more than fusing points of described zirconium-base amorphous alloy 70 ℃), make described molten mixture by being provided with molybdenum filament net (mesh diameter is 0.8 millimeter) thus water the cup filter, and be poured in the melting mould, in argon atmosphere, be cooled to room temperature afterwards, thereby obtain zirconium-base amorphous alloy ingot casting A1, detect by inductively-coupled plasma spectrometer (ICP) and learn that the atom of described zirconium-base amorphous alloy consists of (Zr 55Al 10Cu 30Ni 5) 97(Y 2O 3) 3
Comparative Examples 1
Method according to embodiment 1 prepares zirconium-base amorphous alloy, and different is, according to Zr 55Al 10Cu 30Ni 5Composition preparation compound, make described compound carry out fusion, filtration, cast and cooling then, form as Zr thereby obtain atom 55Al 10Cu 30Ni 5Zirconium-base amorphous alloy ingot casting B1, the detection method that the atom of described zirconium-base amorphous alloy is formed is identical with embodiment 1.
Embodiment 2
Present embodiment is used to illustrate described zirconium-base amorphous alloy provided by the invention and preparation method thereof.
According to Zr 41Ti 14Cu 12.5Ni 10Be 22.5: Y 2O 3: the mol ratio of Zr is about 98: 3.5: thus 1.5 ratios feed intake to mix and obtain mixture, wherein, Ti, Cu, Ni and Be add with the form of high pure metal, and Zr adds Y with the form of zirconium sponge (available from Baotai Huashen Titanium Industry Co., Ltd.) 2O 3Form with oxide compound adds.It is that 25 kilograms intermediate frequency vacuum induction melting furnace (is produced by Sante Vacuum Metallurgical Tech Ind Co., Ltd., Jinzhou City that the mixture that obtains is added to rated capacity, model is ZG-03) the working chamber in, it is 5Pa that described working chamber is evacuated to vacuum tightness, charge into argon gas then, and the vacuum tightness of controlling described working chamber is 40kPa.The melting under the power of 25kW of described mixture is melted to whole, (more than the fusing point at described zirconium-base amorphous alloy 300 ℃) insulation under 1050 ℃ 5 minutes, left standstill then 3 minutes, treat that temperature drops to 830 ℃ (more than fusing points of described zirconium-base amorphous alloy 80 ℃), make described molten mixture by being provided with woven wire (mesh diameter is 1 millimeter) thus water the cup filter, and be poured in the melting mould, in argon atmosphere, be cooled to room temperature afterwards, form as (Zr thereby obtain atom 41Ti 14Cu 12.5Ni 10Be 22.5) 98(Y 2O 3) 2Zirconium-base amorphous alloy ingot casting A2, the detection method that the atom of described zirconium-base amorphous alloy is formed is identical with embodiment 1.
Comparative Examples 2
Method according to embodiment 2 prepares zirconium-base amorphous alloy, and different is, according to Zr 41Ti 14Cu 12.5Ni 10Be 22.5Composition preparation compound, make described compound directly carry out fusion, filtration, cast and cooling then, form as Zr thereby obtain atom 41Ti 14Cu 12.5Ni 10Be 22.5Zirconium-base amorphous alloy ingot casting B2, the detection method that the atom of described zirconium-base amorphous alloy is formed is identical with embodiment 1.
Embodiment 3
Present embodiment is used to illustrate described zirconium-base amorphous alloy provided by the invention and preparation method thereof.
According to Zr 63.5Al 3.6Cu 26Ni 6.9: the mol ratio of MgO: Zr is about 96: 4.8: thus 0.8 ratio feeds intake to mix and obtains mixture, wherein, Al, Cu and Ni add with the form of high pure metal, and Zr adds with the form of zirconium sponge (available from Baotai Huashen Titanium Industry Co., Ltd.), and MgO adds with the form of oxide compound.It is that 25 kilograms intermediate frequency vacuum induction melting furnace (is produced by Sante Vacuum Metallurgical Tech Ind Co., Ltd., Jinzhou City that the mixture that obtains is added to rated capacity, model is ZG-03) the working chamber in, it is 1.5Pa that described working chamber is evacuated to vacuum tightness, charge into argon gas then, and the vacuum tightness of controlling described working chamber is 40kPa.The melting under the power of 25kW of described mixture is melted to whole, (more than the fusing point at described zirconium-base amorphous alloy 100 ℃) insulation under 950 ℃ 5 minutes, left standstill then 3 minutes, treat that temperature drops to 920 ℃ (more than fusing points of described zirconium-base amorphous alloy 70 ℃), make described molten mixture by being provided with molybdenum filament net (mesh diameter is 0.8 millimeter) thus water the cup filter, and be poured in the melting mould, in argon atmosphere, be cooled to room temperature afterwards, form as (Zr thereby obtain atom 63.5Al 3.6Cu 26Ni 6.9) 96(MgO) 4Zirconium-base amorphous alloy ingot casting A3, the detection method that the atom of described zirconium-base amorphous alloy is formed is identical with embodiment 1.
Comparative Examples 3
Method according to embodiment 2 prepares zirconium-base amorphous alloy, and different is, according to Zr 63.5Al 3.6Cu 26Ni 6.9: the mol ratio of Ca is that 96: 4 ratio feeds intake and mixes, and makes resulting compound carry out fusion, filtration, cast and cooling then, forms as (Zr thereby obtain atom 63.5Al 3.6Cu 26Ni 6.9) 96Ca 4Zirconium-base amorphous alloy ingot casting B3, the detection method that the atom of described zirconium-base amorphous alloy is formed is identical with embodiment 1.
Embodiment 4
Present embodiment is used to illustrate described zirconium-base amorphous alloy provided by the invention and preparation method thereof.
According to Zr 62.4Ti 11.2Cu 13.3Ni 9.8Be 3.3: (MgO) 50(CaO) 50: the mol ratio of Zr is about 96: 6: thus 2 ratios feed intake to mix and obtain mixture, wherein, Al, Cu and Ni add with the form of high pure metal, and Zr adds with the form of zirconium sponge (available from Baotai Huashen Titanium Industry Co., Ltd.), and MgO and CaO add with the form of oxide compound.It is that 25 kilograms intermediate frequency vacuum induction melting furnace (is produced by Sante Vacuum Metallurgical Tech Ind Co., Ltd., Jinzhou City that the mixture that obtains is added to rated capacity, model is ZG-03) the working chamber in, it is 4Pa that described working chamber is evacuated to vacuum tightness, charge into argon gas then, and the vacuum tightness of controlling described working chamber is 40kPa.The melting under the power of 25kW of described mixture is melted to whole, (more than the fusing point at described zirconium-base amorphous alloy 300 ℃) insulation under 1050 ℃ 5 minutes, left standstill then 3 minutes, treat that temperature drops to 830 ℃ (more than fusing points of described zirconium-base amorphous alloy 80 ℃), make described molten mixture by being provided with woven wire (mesh diameter is 1 millimeter) thus water the cup filter, and be poured in the melting mould, in argon atmosphere, be cooled to room temperature afterwards, form as (Zr thereby obtain atom 62.4Ti 11.2Cu 13.3Ni 9.8Be 3.3) 96((MgO) 50(CaO) 50) 4Zirconium-base amorphous alloy ingot casting A4, the detection method that the atom of described zirconium-base amorphous alloy is formed is identical with embodiment 1.
Test case
Respectively with the described non-crystaline amorphous metal ingot casting B1-B2 sampling for preparing among the described zirconium-base amorphous alloy ingot casting A1-A4 for preparing among the embodiment 1-4 and the Comparative Examples 1-2, and carry out following performance test:
(1) bending strength test
Make above-mentioned sample become 3 millimeters * 6 millimeters * 15 millimeters sheet material by the electric arc furnace gravity casting respectively, method according to GB/T14452-93, at tonnage is that 1 ton trier (by thinking carefully that newly the model that company produces is the microcomputer control electronics universal testing machine of CMT5105) is gone up the bending strength that detects the sheet material that above-mentioned sample makes, its test condition comprises: span is 50 millimeters, loading velocity is 0.5 mm/min, and its test result is as shown in table 1; The stress-strain curve that obtains corresponding zirconium-base amorphous alloy sample simultaneously as shown in Figure 1, and the maximum plastic strain of corresponding each described sample of acquisition, its result is as shown in table 1 below.
(2) impelling strength test
Make above-mentioned sample become 3 millimeters * 6 millimeters * 15 millimeters sheet material by the electric arc furnace gravity casting respectively, utilize the impelling strength of the described sheet material of ZBC1251-2 balance weight impact testing machine (being produced by the Shenzhen Sans Material Detection Co., Ltd) test then, its test result is as shown in table 1.
(3) XRD analysis
The employing model is that the x-ray powder diffraction instrument of D-MAX2200PC carries out XRD analysis to zirconium-base amorphous alloy A1 and A2, and its test condition comprises: with copper target emanation, incident wavelength
Figure G2009102543976D00101
Acceleration voltage is 40KV, and electric current is 20 milliamperes, adopts step-scan, and scanning step is 0.04 °.Resulting XRD diffracting spectrum as shown in Figure 2, as seen from Figure 2, described zirconium-base amorphous alloy provided by the invention has very big amorphous formation ability.
Table 1
Sample Bending strength (MPa) Maximum plastic strain (%) Impelling strength (KJ/m 2)
A1 2780 4.1 110
A2 2676 3.3 98
A3 2533 3.6 88
A4 2574 3.9 91
B1 2133 2.3 66
B2 2311 1.8 71
B3 2405 2.6 80
As can be seen from Table 1, adopt the prepared described zirconium-base amorphous alloy of described zirconium-base amorphous preparation method provided by the invention to have very high bending strength, maximum plastic strain and impelling strength, thereby have good toughness.

Claims (10)

1. a zirconium-base amorphous alloy is characterized in that, the general formula of this zirconium-base amorphous alloy is as (Zr aM bN c) 100-xQ x, wherein, M is at least a transition metal except that zirconium, and N is Be or Al, and Q is CaO, MgO, Y 2O 3, Nd 2O 3In at least a, a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, a+b+c=100,1≤x≤15.
2. zirconium-base amorphous alloy according to claim 1, wherein, M is at least two kinds among Ti, Ni, the Cu.
3. zirconium-base amorphous alloy according to claim 1, wherein, 50≤a≤70,25≤b≤35,3≤c≤23,2≤x≤5.
4. the preparation method of a zirconium-base amorphous alloy is characterized in that, this method comprises Zr, M, N and Q according to Zr aM bN c: the mol ratio of Q: Zr is the mixed of 100-x: x+y: y, carry out fusion, filtration, cast and cooling then successively, thereby the general formula of the zirconium-base amorphous alloy that makes is as (Zr aM bN c) 100-xQ x, wherein, M is at least a transition metal except that zirconium, and N is Be or Al, and Q is CaO, MgO, Y 2O 3, Nd 2O 3In at least a, a, b, c are atomic percent, and 45≤a≤75,20≤b≤40,1≤c≤25, a+b+c=100,1≤x≤15,0.1≤y≤5.
5. method according to claim 4, wherein, M is at least two kinds among Ti, Ni, the Cu.
6. method according to claim 4, wherein, 50≤a≤70,25≤b≤35,3≤c≤23,2≤x≤5,0.2≤y≤2.
7. method according to claim 4, wherein, described being melted in the smelting furnace with working chamber carried out, described fused method is included under the above temperature more than 100 ℃ of fusing point of described zirconium-base amorphous alloy, it is 0.1-10Pa that described working chamber is evacuated to vacuum tightness, and charging into rare gas element to vacuum tightness then is 30-50kPa.
8. method according to claim 7, wherein, under the above 100-300 of fusing point that described fused method is included in described zirconium-base amorphous alloy ℃ the temperature, it is 0.5-5Pa that described working chamber is evacuated to vacuum tightness, and charging into rare gas element to vacuum tightness then is 35-45kPa.
9. method according to claim 4, wherein, described filtration is by making the melt that obtains after the described fusion through high temperature resistant net, and the mesh diameter of described high temperature resistant net is the 0.5-5 millimeter.
10. method according to claim 4, wherein, the condition of described cast comprises: temperature is the above 30-80 of the fusing point of described zirconium-base amorphous alloy ℃, protection of inert gas.
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Application Number Priority Date Filing Date Title
CN2009102543976A CN102108474B (en) 2009-12-28 2009-12-28 Zirconium-based amorphous alloy and preparation method thereof
EP10829516.3A EP2499270B1 (en) 2009-11-11 2010-11-08 Zirconium-based amorphous alloy, preparing method and recycling method thereof
PCT/CN2010/078525 WO2011057552A1 (en) 2009-11-11 2010-11-08 Zirconium-based amorphous alloy, preparing method and recycling method thereof
US12/941,416 US8603266B2 (en) 2009-11-11 2010-11-08 Amorphous alloys having zirconium and methods thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534437A (en) * 2011-12-15 2012-07-04 比亚迪股份有限公司 Amorphous alloy and method for preparing same
WO2014101654A1 (en) * 2012-12-31 2014-07-03 深圳市比亚迪汽车研发有限公司 Use of a noncrystalline alloy material source, composite material, and method of preparing the composite material
CN103938131A (en) * 2014-03-27 2014-07-23 安徽华兴金属有限责任公司 Amorphous alloy composition and preparation method thereof
CN104694781A (en) * 2013-12-06 2015-06-10 斯沃奇集团研究和开发有限公司 Bulk amorphous alloy made of beryllium-free zirconium
CN105132687A (en) * 2015-09-15 2015-12-09 宋佳 Recovery method of zircon-based amorphous alloy

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534437A (en) * 2011-12-15 2012-07-04 比亚迪股份有限公司 Amorphous alloy and method for preparing same
WO2014101654A1 (en) * 2012-12-31 2014-07-03 深圳市比亚迪汽车研发有限公司 Use of a noncrystalline alloy material source, composite material, and method of preparing the composite material
CN104694781A (en) * 2013-12-06 2015-06-10 斯沃奇集团研究和开发有限公司 Bulk amorphous alloy made of beryllium-free zirconium
CN103938131A (en) * 2014-03-27 2014-07-23 安徽华兴金属有限责任公司 Amorphous alloy composition and preparation method thereof
CN103938131B (en) * 2014-03-27 2016-01-20 安徽华兴金属有限责任公司 A kind of non-crystaline amorphous metal composition and preparation method
CN105132687A (en) * 2015-09-15 2015-12-09 宋佳 Recovery method of zircon-based amorphous alloy

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