CN104745973A - Zr-based amorphous alloy and manufacturing method thereof - Google Patents

Zr-based amorphous alloy and manufacturing method thereof Download PDF

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CN104745973A
CN104745973A CN201310731855.7A CN201310731855A CN104745973A CN 104745973 A CN104745973 A CN 104745973A CN 201310731855 A CN201310731855 A CN 201310731855A CN 104745973 A CN104745973 A CN 104745973A
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zirconium
alloy
amorphous alloy
base amorphous
metal
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张法亮
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BYD Co Ltd
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BYD Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

The invention discloses a zr-based amorphous alloy and a manufacturing method of the zr-based amorphous alloy. The zr-based amorphous alloy is composed of ZraCubAlcMd (Erl-xYx) e, wherein the M is selected from at least one of Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta, and according to the atomic percentage of elements of a, b, c, d and e in zr-based amorphous alloy, a is larger than or equal to 40 and smaller than or equal to 70, b is larger than or equal to 15 and smaller than or equal to 35, c is larger than or equal to 5 and small than or equal to 15, d is larger than or equal to 2 and smaller than or equal to 15, and e is larger than 0.2 and smaller than or equal to 2.5; and the atom molar ratio of Er and Y meets the formula that x is larger than 0 and smaller than 0.5. According to the zr-based amorphous alloy, the amorphous forming capacity can be improved, the larger critical dimension is obtained, and the mechanical performance influence is small.

Description

A kind of zirconium-base amorphous alloy and preparation method thereof
Technical field
The present invention relates to a kind of zirconium-base amorphous alloy and preparation method thereof.
Background technology
Non-crystaline amorphous metal comes across the eighties of last century sixties.Initial non-crystaline amorphous metal can only reach micron order due to the critical size overall dimension of amorphous (formed), and is difficult to obtain practical application.But the material properties such as the high strength that non-crystaline amorphous metal has, high rigidity, corrosion-resistant and excellent temperature flowing have attracted vast researcher constantly to study, and in succession have developed large critical size and be suitable for the non-crystaline amorphous metal of suitability for industrialized production, its critical size develops into grade from micron order gradually notably can reach centimetre-sized.Under normal circumstances critical cooling rate is less than 500 DEG C/s, the non-crystaline amorphous metal that critical size is greater than 1mm is called bulk amorphous alloys.The suitability for industrialized production that appears as of bulk amorphous alloys provides possibility.
But, the amorphous formation ability of current non-crystaline amorphous metal is easy to the impact being subject to non-metallic element or impurity element, cause the significantly reduction of non-crystaline amorphous metal critical size even cannot form amorphous, especially the nonmetal elemental gas such as oxygen nitrogen significantly can worsen critical size (document 1, Weihua Wang, Progress inMaterials Science, Vol52, Issue4, May2007, page:540-596).Therefore, when manufacturing non-crystaline amorphous metal, usually very harsh requirement is had to raw-material purity, and the environment smelted also is required very strict, even need (document 2, C.T.Liuetc under the preparation condition of high vacuum, Metallurgical and Materials Transaction A, Vol29A, 1998, page:1811-1820).Therefore, considerably increase the cost of current non-crystaline amorphous metal actual production, and be difficult to popularization and carry out suitability for industrialized production.
US6682611B2 discloses a kind of non-crystaline amorphous metal, and this non-crystaline amorphous metal is doped element Y in Zr-Cu-Al-Ni quad alloy.Although this invention greatly reduces requirement to material purity for some specific zirconium-base amorphous alloy by adding Y element, but the interpolation of unsuitable Y element is easy to the deterioration of the mechanical property of the non-crystaline amorphous metal causing preparation, and then affect the engineer applied of non-crystaline amorphous metal.
As can be seen here, in order to realize the suitability for industrialized production of non-crystaline amorphous metal, needing the non-crystaline amorphous metal improved, reducing current non-crystaline amorphous metal and producing requirement to starting material and preparation condition, and the impact on non-crystaline amorphous metal mechanical property can be reduced.Therefore, need a kind of new non-crystaline amorphous metal, can suitability for industrialized production be suitable for.
Summary of the invention
Problem high to material purity requirement when the object of the invention is to overcome prior art production non-crystaline amorphous metal, provides a kind of zirconium-base amorphous alloy and preparation method thereof.
To achieve these goals, the invention provides a kind of zirconium-base amorphous alloy, wherein, consisting of of this zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e; Wherein, M is selected from least one in Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.2 < e≤2.5; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
Present invention also offers a kind of method preparing zirconium-base amorphous alloy; under the method is included in protection of inert gas or under vacuum condition; the raw material of zirconium-base amorphous alloy is carried out melting and cooling forming; wherein; the raw material of described zirconium-base amorphous alloy comprises Zr, Cu, Al, Er, Y and M, consisting of of the zirconium-base amorphous alloy formed by the raw material of described zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e, wherein, M is selected from least one in Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.2 < e≤2.5; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
Er element is added in the composition of zirconium-base amorphous alloy provided by the invention, and Er and Y combines with specified proportion, not only can improve the amorphous formation ability of this non-crystaline amorphous metal, the critical size of acquisition is larger, and less to the mechanical impact of this non-crystaline amorphous metal.Zirconium-base amorphous alloy provided by the invention is more conducive to the suitability for industrialized production manufacture of non-crystaline amorphous metal in addition, such as, can allow higher magazine elemental gas content, greatly reduces the requirement to smelting vacuum environment; The requirement to material purity can be reduced, the zirconium material of technical grade can be selected, can greatly fall low-alloyed material cost.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of zirconium-base amorphous alloy, wherein, consisting of of this zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e; Wherein, M is selected from least one in Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.2 < e≤2.5; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
Although introduce rare earth element can reduce requirement to raw-material purity in zirconium-base amorphous alloy, improve the amorphous formation ability of zirconium-base amorphous alloy, but the amorphous formation ability of zirconium-base amorphous alloy to the kind of the rare earth element added in non-crystaline amorphous metal and quantity very responsive, and the kind of rare earth element of adding and quantity can produce material impact to the mechanical property of non-crystaline amorphous metal.
As in prior art document, although add the amorphous formation ability that rare earth element y can improve non-crystaline amorphous metal significantly, and the critical size of non-crystaline amorphous metal can be improved, but add excessive rare earth element y, significantly can reduce the mechanical property of the zirconium-base amorphous alloy obtained, and be unfavorable for the engineer applied of non-crystaline amorphous metal.
In zirconium-base amorphous alloy provided by the invention, introduce rare earth element er, and Er and Y combines with specified proportion, the amorphous formation ability of this zirconium-base amorphous alloy also effectively can be improved, and can much smaller than adding rare earth element y separately on the impact of the mechanical property of this zirconium-base amorphous alloy.Preferably, the consisting of of this zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e; Wherein, M is selected from least one in Ni, Fe, Co, Ti and Hf; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.3 < e≤2; Atomic molar between Er and Y is than meeting 0 < x < 0.5.The zirconium-base amorphous alloy of this composition can have better amorphous formation ability, can use technical grade starting material, thus reduces the cost producing non-crystaline amorphous metal.Even and if using the zirconium-base amorphous alloy oxygen level with above-mentioned composition high, the flexural strength still had, reducing the manufacture requirements to producing non-crystaline amorphous metal, having better industrial production application prospect.
According to the preferred embodiment of the present invention, under preferable case, consisting of of described zirconium-base amorphous alloy: Zr 51.9cu 30al 10ni 7(Er 0.91y 0.09) 1.1, Zr 51cu 30al 10ni 7hf 1(Er 0.8y 0.2) 1, Zr 50cu 30al 10ni 6.5hf 1ti 0.5(Er 0.75y 0.25) 2, Zr 51cu 27al 8ni 7co 3hf 0.8fe 2.5ti 0.49(Er 0.52y 0.48) 0.21, Zr 51.5cu 29al 10ni 7(Er 0.8y 0.2) 2.5or Zr 65cu 21al 8ni 5(Er 0.6y 0.4) 1.
In the present invention, in described zirconium-base amorphous alloy composition, when M is a kind of element, d represents the atomic percent that this element is corresponding in described zirconium-base amorphous alloy, as Zr 51.9cu 30al 10ni 7(Er 0.91y 0.09) 1.1, wherein M is selected from Ni.When M is selected from element of more than two kinds, d represents the atomic percent sum of often kind of element correspondence in this zirconium-base amorphous alloy that M selects, as Zr 50cu 30al 10ni 6.5hf 1ti 0.5(Er 0.75y 0.25) 2, wherein M is selected from Ni, Hf and Ti, d be the atomic percent 6.5,1 and 0.5 that Ni, Hf and Ti are respectively corresponding in zirconium-base amorphous alloy and, i.e. d=6.5+1+0.5=8.
Rare earth element er is added in the composition of zirconium-base amorphous alloy provided by the invention, and rare earth element er and Y combine with specified quantitative, the amorphous formation ability of this zirconium-base amorphous alloy can be improved, the content containing impurity element especially foreign gas element can being allowed to compare when adding separately rare earth element y higher, greatly reducing the requirement to smelting vacuum environment.Under preferable case, in described zirconium-base amorphous alloy, oxygen element content is below 1000ppm.
According to the present invention, add in the composition of the zirconium-base amorphous alloy provided with the rare earth element er of specified quantitative combination and Y, in this zirconium-base amorphous alloy, can impurity element be there is.Under preferable case, with the total amount of described zirconium-base amorphous alloy for benchmark, in described zirconium-base amorphous alloy, the atomic percent of metallic impurity elements is less than 2%.
According to the present invention, the amorphous formation ability of described zirconium-base amorphous alloy improves, and under preferable case, the critical size of described zirconium-base amorphous alloy is more than 3mm.
Present invention also offers a kind of method preparing zirconium-base amorphous alloy; under the method is included in protection of inert gas or under vacuum condition; the raw material of zirconium-base amorphous alloy is carried out melting and cooling forming; wherein; the raw material of described zirconium-base amorphous alloy comprises Zr, Cu, Al, Er, Y and M, consisting of of the zirconium-base amorphous alloy formed by the raw material of described zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e, wherein, M is selected from least one in Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.2 < e≤2.5; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
According to the present invention, preferably, the consisting of of zirconium-base amorphous alloy of formation: Zr acu bal cm d(Er 1-xy x) e, wherein, M is selected from least one in Ni, Fe, Co, Ti and Hf; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.3 < e≤2; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
According to the present invention, the raw material of described zirconium-base amorphous alloy can select the starting material of the non-crystaline amorphous metal of low-purity to carry out the manufacturing of described zirconium-base amorphous alloy.Under preferable case, the purity of the raw material of described zirconium-base amorphous alloy is technical grade, and wherein, the purity of Zr, Cu, Al and M metal is more than 99 % by weight.As zirconium material can select the HZr-1 of technical grade, and provide the starting material of Cu, Al and M metal can adopt purity be more than 99 % by weight technical grade raw material metal.In addition, described zirconium-base amorphous alloy does not need the interpolation of element S c expensive in prior art, thus greatly reduces the material cost of alloy.In addition, rare earth metal also can choose the raw material of low-purity, and under preferable case, the purity of Er and Y is more than 98 % by weight.Consider that rare earth element is oxidizable element, mixing for ease of carrying out smelting with mother alloy simultaneously, preferably adding rare earth element with the form of master alloy.Under preferable case, when carrying out described melting, adding of Er and Y adopts the form of AlRE alloy to add, and RE is the combination of rare earth element y and Er.
According to the present invention, prepare zirconium-base amorphous alloy to add rare earth element er and can improve amorphous alloy forming ability, the oxygen level that there is below 1000ppm is allowed in the zirconium-base amorphous alloy of preparation, the requirement to vacuum environment when carrying out melting can be reduced, under preferable case, when carrying out described melting to the requirement of vacuum condition for being less than 500Pa.
According to the present invention, described protection of inert gas or vacuum condition are to make alloy raw material obtain protection in fusion process, avoiding oxidized.The antioxidant property of non-crystaline amorphous metal raw material of the present invention is better, therefore lower to the requirement of protection of inert gas or vacuum condition.Described rare gas element is one or more in the periodic table of elements in neutral element gas.The purity of described rare gas element is not less than 95% volume percent, such as, can be 95-99.99% volume percent.Under preferable case, the vacuum tightness of described vacuum condition for being less than 500Pa, preferably can be less than 100Pa.
According to the present invention, the method of described melting can be the melting method of various routine in this area, as long as by abundant for non-crystaline amorphous metal raw material melting, under preferable case, described melting can be vacuum induction melting, vacuum arc melting or the melting of vacuum consumable formula electrode.Described melting can be carried out in melting equipment, and smelting temperature and smelting time have some changes with the raw-material difference of non-crystaline amorphous metal, and in the present invention, smelting temperature can be 1000-1500 DEG C; Smelting time can be 10-50 minute, is preferably 10-30 minute.Described melting equipment can be conventional melting equipment, such as vacuum arc melting furnace, vacuum induction melting furnace or vacuum resistance furnace.
In the present invention, the glass-forming ability of the zirconium-base amorphous alloy provided is strong, and described cooling forming can adopt the pressure die casting forming method of various routine in this area, such as, alloy material (melt) pressure die casting of melting in mould, is then cooled.Described pressure casting processes can be gravitational casting, negative pressure casting, malleation casting, any one in high-pressure casting, and casting condition, if casting pressure is conventionally known to one of skill in the art, such as, the pressure of high-pressure casting can be 2-20MPa.Described gravity casting refers to and utilizes the action of gravity of melt itself to be cast in mould.The concrete operation method of described casting is conventionally known to one of skill in the art.Such as, moulding stock can for copper alloy, stainless steel and thermal conductivity be that 30-400W/mK(is preferably 50-200W/mK) various die steel materials.Mould can carry out water-cooled, oil cooling.Do not specially require the degree of cooling, as long as can be shaped to non-crystaline amorphous metal of the present invention, rate of cooling can be more than 500K/s.
Below will be described the present invention by embodiment.
XRD diffractometer (Rigaku D/Max2200PC) is adopted to analyze whether the alloy prepared in following examples and comparative example is amorphous.Analysis condition is copper target, incident wavelength λ=1.54060 , acceleration voltage is 40kV, and electric current is 20mA, and adopt step-scan, scanning step is 0.04 °.
Adopt XRD diffractometer (Rigaku D/Max2500PC) to analyze the critical size of the non-crystaline amorphous metal of preparation, angle of diffraction 2 θ is between 20 °-60 °, and sweep velocity is 4 °/min, and sweep voltage is 40kV, and electric current is 200mA.
Adopt the oxygen level in the non-crystaline amorphous metal of oxygen and nitrogen content tester (Beijing Nanogram Corp. IRO-II determination of oxygen by infrared analysis instrument) measurement preparation, accuracy of instrument is RSD≤0.5 % by weight, and shielding gas is high-purity Ar.
According to inductively coupled plasma emission spectrography, adopt the composition in the non-crystaline amorphous metal of Induction Couple Plasma (ICP-AES) (Thermo Electron Corp. of the U.S., model TEVA) analysis preparation.
According to ISO6892.1-2009 method, omnipotent test machine for mechanism (INSTRON company) is adopted to measure the flexural strength of the non-crystaline amorphous metal of preparation.
Embodiment 1
The present embodiment illustrates zirconium-base amorphous alloy Zr provided by the invention 51.9cu 30al 10ni 7(Er 0.91y 0.09) 1.1preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The elemental metals that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Er, Y adopt purity to be greater than 99 % by weight.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample A1.
Alloy sample A1 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A1 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A1, the results are shown in Table 1.
The oxygen level of beta alloy sample A1 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A1.
Get alloy part sample A1, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Embodiment 2
The present embodiment illustrates zirconium-base amorphous alloy Zr provided by the invention 51cu 30al 10ni 7hf 1(Er 0.8y 0.2) 1preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The technical grade HZr-1 zirconium material that metal zirconium adopts metal (Zr+Hf) purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Hf, Er, Y adopt purity to be greater than 99 % by weight, Er and Y adopts AlErY master alloy.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample A2.
Alloy sample A2 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A2 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A2, the results are shown in Table 1.
The oxygen level of beta alloy sample A2 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A2.
Get alloy part sample A2, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Embodiment 3
The present embodiment illustrates zirconium-base amorphous alloy Zr provided by the invention 50cu 30al 10ni 6.5hf 1ti 0.5(Er 0.75y 0.25) 2preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The technical grade HZr-1 zirconium material that metal zirconium adopts metal (Zr+Hf) purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Hf, Er, Y adopt purity to be greater than 99 % by weight, Er and Y adopts AlErY master alloy, and Ti adopts AlTi master alloy.
The alloy sample of melting to be casted in metal die (wherein by the method for high-pressure casting, pressure 20MPa, moulding stock SKD61), and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and the high truncated cone-shaped metal founding for 20mm is designated as alloy sample A3.
Alloy sample A3 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A3 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A3, the results are shown in Table 1.
The oxygen level of beta alloy sample A3 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A3.
Get alloy part sample A3, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Embodiment 4
The present embodiment illustrates zirconium-base amorphous alloy Zr provided by the invention 51cu 27al 8ni 7co 3hf 0.8fe 2.5ti 0.49(Er 0.52y 0.48) 0.21preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The technical grade HZr-1 zirconium material that metal zirconium adopts metal (Zr+Hf) purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Hf, Er, Y adopt purity to be greater than 99 % by weight, Er and Y adopts AlErY master alloy, Fe and Ti adopts the master alloy containing aluminium respectively.
The alloy sample of melting to be casted in metal die (wherein by the method for high-pressure casting, pressure 20MPa, moulding stock SKD61), and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and the high truncated cone-shaped metal founding for 20mm is designated as alloy sample A4.
Alloy sample A4 being carried out XRD powder diffraction analysis, for occurring that peak type is the diffraction peak at steamed bun peak in the XRD spectra obtained, illustrating that alloy sample A4 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A4, the results are shown in Table 1.
The oxygen level of beta alloy sample A4 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A4.
Get alloy part sample A4, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Embodiment 5
The present embodiment illustrates zirconium-base amorphous alloy Zr provided by the invention 51.5cu 29al 10ni 7(Er 0.8y 0.2) 2.5preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The zirconium material that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Er, Y adopt purity to be greater than 99 % by weight, Er and Y adopts AlErY master alloy.
The alloy sample of melting to be casted in metal die (wherein by the method for high-pressure casting, pressure 20MPa, moulding stock SKD61), and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and the high truncated cone-shaped metal founding for 20mm is designated as alloy sample A5.
Alloy sample A5 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A5 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A5, the results are shown in Table 1.
The oxygen level of beta alloy sample A5 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A5.
Get alloy part sample A5, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Embodiment 6
The present embodiment illustrates zirconium-base amorphous alloy Zr provided by the invention 65cu 21al 8ni 5(Er 0.6y 0.4) 1preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The zirconium material that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Er, Y adopt purity to be greater than 99 % by weight, Er and Y adopts AlErY master alloy.
The alloy sample of melting to be casted in metal die (wherein by the method for high-pressure casting, pressure 20MPa, moulding stock SKD61), and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and the high truncated cone-shaped metal founding for 20mm is designated as alloy sample A6.
Alloy sample A6 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample A1 is non-crystaline amorphous metal.
Measure the critical size of alloy sample A6, the results are shown in Table 1.
Beta alloy sample A6 oxygen level and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample A6.
Get alloy part sample A6, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Comparative example 1
This comparative example illustrates zirconium-base amorphous alloy Zr 51.9cu 30al 10ni 7er 1.1preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The zirconium material that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Er adopt purity to be greater than 99 % by weight, Er adopts AlEr master alloy.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample D1.
Alloy sample D1 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample D1 is non-crystaline amorphous metal.
Measure the critical size of alloy sample D1, the results are shown in Table 1.
The oxygen level of beta alloy sample D1 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample D1.
Get alloy part sample D1, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Comparative example 2
This comparative example illustrates zirconium-base amorphous alloy Zr 51.5cu 30al 10ni 7hf 1er 0.5preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The technical grade HZr-1 zirconium material that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Hf, Er adopt purity to be greater than 99 % by weight, Er adopts AlEr master alloy.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample D2.
Alloy sample D2 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample D2 is non-crystaline amorphous metal.
Measure the critical size of alloy sample D2, the results are shown in Table 1.
The oxygen level of beta alloy sample D2 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample D2.
Get alloy part sample D2, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Comparative example 3
This comparative example illustrates zirconium-base amorphous alloy Zr 51cu 29al 10hf 1ni 7y 2preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The technical grade HZr-1 zirconium material that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Hf, Y adopt purity to be greater than 99 % by weight, Y adopts AlY master alloy.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample D3.
Alloy sample D3 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample D3 is non-crystaline amorphous metal.
Measure the critical size of alloy sample D3, the results are shown in Table 1.
The oxygen level of beta alloy sample D3 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample D3.
Get alloy part sample D3, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Comparative example 4
This comparative example illustrates zirconium-base amorphous alloy Zr 52.9cu 30al 10ni 7(Er 0.67y 0.33) 0.15preparation method.
Each component raw material is dropped in vacuum melting furnace, and vacuumizes as 50Pa, then pass into purity be the argon gas of 99.99% volume percent as shielding gas, carry out alloy melting, smelting temperature is 1100 DEG C, and smelting time is 15 minutes, makes the abundant melting of alloy raw material.Then turn over molten 3 times, make its abundant alloying.Smelting temperature in fusion process adopts infrared measurement of temperature test to obtain.
The zirconium material that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Er, Y adopt purity to be greater than 99 % by weight, Er and Y adopts AlErY master alloy.
Dropped in vacuum melting furnace by metal after proportioning, and the argon gas being filled with 99.99% carries out atmosphere protection, carry out alloying smelting, smelting temperature is 1100 DEG C, and tap to tap time is 15Min.Smelting temperature in smelting process adopts infrared measurement of temperature test to obtain.
The alloy sample of melting is casted into (wherein, pressure 20MPa, moulding stock SKD61) in metal die by the method for high-pressure casting, and cool with the rate of cooling of 1000K/s, acquisition diameter is 2-20mm, and height is the truncated cone-shaped metal founding of 20mm, is designated as alloy sample D4.
Alloy sample D4 is carried out XRD powder diffraction analysis, in the XRD spectra obtained, occurs that peak type is the diffraction peak at steamed bun peak, illustrate that alloy sample D4 is non-crystaline amorphous metal.
Measure the critical size of alloy sample D4, the results are shown in Table 1.
The oxygen level of beta alloy sample D4 and moiety, the massfraction being analyzed contained metallic element in the alloy that obtains by ICP-AES is converted into atomic percent, and the results are shown in Table 1 for the amorphous alloy component of alloy sample D4.
Get alloy part sample D4, put into vacuum die casting equipment and be expelled to mould, and cool with the rate of cooling of 500K/s, obtain the sheet material of 1.5mm × 6mm × 12mm, measure its flexural strength, the results are shown in Table 1.
Comparative example 5
According to the method for comparative example 4, unlike, substitute " elemental metals that metal zirconium adopts metal purity to be greater than 99 % by weight, the elemental metals that Al, Cu, Ni, Er, Y adopt purity to be greater than 99 % by weight " with " elemental metals that metal zirconium adopts metal purity to be greater than 99.9 % by weight; elemental metals that Al, Cu, Ni, Er, Y adopt purity to be greater than 99.9 % by weight ".
Obtain alloy sample D5, the critical size of alloy, oxygen level, moiety and flexural strength the results are shown in Table 1.
Table 1
As can be seen from the data results of above-described embodiment, comparative example and table 1, zirconium-base amorphous alloy provided by the invention is adopted to improve amorphous formation ability, larger critical size can be obtained in the raw-material situation of use technical grade, and still there is when oxygen level is high height flexural strength, illustrate that non-crystaline amorphous metal provided by the invention is little to the severity manufacturing process entails, oxygen level is little to mechanical impact.Particularly in the composition of described zirconium-base amorphous alloy containing specified proportion combination rare earth element er and Y(Er and Y between atomic molar than meet 0 < x < 0.5) and ErY combination atomic percent meet 0.3 < e≤2 time can have better effect, namely larger critical size, and flexural strength numerical value is also high simultaneously.
Comparative example 1-3 does not adopt the particular combination of Er and Y.Wherein comparative example 1 compares embodiment 1 and comparative example 2 compares embodiment 2, only has Er in the composition of the non-crystaline amorphous metal in comparative example, uses the critical size of alloy sample D1 and D2 obtained during industrial raw material to be all less than alloy sample A1 and A2 of embodiment 1 and 2.Comparative example 3 compares embodiment 1, only has Y in the composition of non-crystaline amorphous metal, even if use the alloy sample D3 oxygen level obtained during industrial raw material low, flexural strength is also not as the alloy sample A1 of embodiment 1.Although also have Er and Y in the non-crystaline amorphous metal of comparative example 4, the atomic percent of ErY combination is not in the specific scope of the present invention institute, and the critical size of the alloy sample D4 therefore obtained during use industrial raw material is little and flexural strength is poor.Comparative example 5 needs to use starting material higher than comparative example 4 purity, just can obtain large critical size and high bending strength simultaneously, but like this in actual industrialization is produced the manufacturing cost of non-crystaline amorphous metal will significantly increase, there is no actual suitability for industrialized production meaning.
Use in embodiment 1-6 during zirconium-base amorphous alloy provided by the invention and can adopt technical grade starting material, the requirement of the vacuum condition to melting during preparation can be reduced, the Commercialization application of suitability for industrialized production preparation and product can be conducive to.

Claims (10)

1. a zirconium-base amorphous alloy, is characterized in that, consisting of of this zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e; Wherein, M is selected from least one in Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.2 < e≤2.5; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
2. zirconium-base amorphous alloy according to claim 1, wherein, M is selected from least one in Ni, Fe, Co, Ti and Hf; E meets 0.3 < e≤2.
3. zirconium-base amorphous alloy according to claim 2, wherein, consisting of of described zirconium-base amorphous alloy: Zr 51.9cu 30al 10ni 7(Er 0.91y 0.09) 1.1, Zr 51cu 30al 10ni 7hf 1(Er 0.8y 0.2) 1, Zr 50cu 30al 10ni 6.5hf 1ti 0.5(Er 0.75y 0.25) 2, Zr 51cu 27al 8ni 7co 3hf 0.8fe 2.5ti 0.49(Er 0.52y 0.48) 0.21, Zr 51.5cu 29al 10ni 7(Er 0.8y 0.2) 2.5or Zr 65cu 21al 8ni 5(Er 0.6y 0.4) 1.
4., according to the zirconium-base amorphous alloy in claim 1-3 described in any one, wherein, with the total amount of described zirconium-base amorphous alloy for benchmark, in described zirconium-base amorphous alloy, the atomic percent of metallic impurity elements is less than 2%.
5. according to the zirconium-base amorphous alloy in claim 1-3 described in any one, wherein, the critical size of described zirconium-base amorphous alloy is more than 3mm.
6. according to the zirconium-base amorphous alloy in claim 1-3 described in any one, wherein, in described zirconium-base amorphous alloy, oxygen element content is below 1000ppm.
7. prepare the method for zirconium-base amorphous alloy for one kind; under the method is included in protection of inert gas or under vacuum condition; the raw material of zirconium-base amorphous alloy is carried out melting and cooling forming; it is characterized in that; the raw material of described zirconium-base amorphous alloy comprises Zr, Cu, Al, Er, Y and M, consisting of of the zirconium-base amorphous alloy formed by the raw material of described zirconium-base amorphous alloy: Zr acu bal cm d(Er 1-xy x) e, wherein, M is selected from least one in Ni, Fe, Co, Mn, Cr, Ti, Hf and Ta; A, b, c, d and e are the atomic percent that each element is corresponding in this zirconium-base amorphous alloy, are respectively: 40≤a≤70,15≤b≤35,5≤c≤15,3≤d≤15,0.2 < e≤2.5; Atomic molar between Er and Y is than meeting 0 < x < 0.5.
8. method according to claim 7, wherein, M is selected from least one in Ni, Fe, Co, Ti and Hf; E meets 0.3 < e≤2.
9. the method according to claim 7 or 8, wherein, the purity of the raw material of described zirconium-base amorphous alloy is technical grade, wherein, the purity of Zr, Cu, Al and M metal be more than 99 % by weight, Er and Y purity be more than 98 % by weight.
10. method according to claim 7, wherein, when carrying out described melting, adding of Er and Y adopts the form of AlRE alloy to add, and RE is the combination of Er and Y.
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