CN103484800B - A kind of zirconium-base amorphous alloy and preparation method thereof - Google Patents
A kind of zirconium-base amorphous alloy and preparation method thereof Download PDFInfo
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- CN103484800B CN103484800B CN201310410770.9A CN201310410770A CN103484800B CN 103484800 B CN103484800 B CN 103484800B CN 201310410770 A CN201310410770 A CN 201310410770A CN 103484800 B CN103484800 B CN 103484800B
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000005300 metallic glass Substances 0.000 claims abstract description 13
- 239000007858 starting material Substances 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims description 32
- 230000008018 melting Effects 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000003723 Smelting Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052704 radon Inorganic materials 0.000 claims description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004512 die casting Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/022—Casting heavy metals, with exceedingly high melting points, i.e. more than 1600 degrees C, e.g. W 3380 degrees C, Ta 3000 degrees C, Mo 2620 degrees C, Zr 1860 degrees C, Cr 1765 degrees C, V 1715 degrees C
-
- 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
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Continuous Casting (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to metallic substance and metallurgical technology field, relate to a kind of amorphous alloy material, be specifically related to a kind of zirconium-base amorphous alloy and preparation method thereof.The present invention is by the atomic percentage conc of each component in adjustment zirconium-base amorphous alloy, and in zirconium-base amorphous alloy, add non-metallic element Y, Sc, the preparation requirement of this non-crystaline amorphous metal can be reduced, the more important thing is under the prerequisite keeping over-all properties not decline, greatly reduce the high request to material purity, allow to retain a certain amount of impurity element in starting material simultaneously.Therefore, by suitably adjusting the ratio of the non-metallic element such as Si, C in non-crystaline amorphous metal, the over-all properties of zirconium-base amorphous alloy can not be affected, the pressure of material cost during industrialized mass production can be reduced on the contrary.Can also obtain the bulk zirconium-base amorphous alloy of critical size at more than 3mm by preparation method of the present invention, this zirconium-base amorphous alloy not only has excellent mechanical property, simultaneously lower to the content requirement of material purity and impurity element.
Description
Technical field
The invention belongs to metallic substance and metallurgical technology field, relate to a kind of amorphous alloy material, be specifically related to a kind of zirconium-base amorphous alloy and preparation method thereof.
Background technology
Amorphous alloy material is owing to having the special construction of longrange disorder and short range order, thus there is the performance that high strength, high rigidity, wear resistance, solidity to corrosion, larger elastic limit and higher resistive etc. are superior, but also show the features such as excellent supraconductivity and low magnetic loss, therefore amorphous alloy material is considered to the potential new structural material of most, thus is widely applied to the fields such as machinery, medical treatment, IT electronics, military project.
For keeping the integrity of amorphous structure, traditional non-crystaline amorphous metal is higher to the factors dictate such as material purity, preparation condition.Through years of researches, it is found that zirconium-base amorphous alloy has excellent amorphous formation ability, by the control of composition, can decrease to the restriction of material purity and preparation condition.Such as material purity requires more than 99.9% (mass ratio).In preparation process, need very high vacuum tightness environment, melting atmosphere requirements reaches condition of high vacuum degree 10
~ 4~ 10
~ 3pa, a small amount of oxygen or other impurity all will greatly fall low-alloyed amorphous formation ability.In the non-crystaline amorphous metal preparation process of routine, due to the limited extent reduced, harsh production process considerably increases the production cost of amorphous alloy product, and this kind of zirconium-base amorphous alloy is still stopped under lab, cannot produce in batches, thus limit the widespread use of non-crystaline amorphous metal.
Summary of the invention
Discovery is studied through the present inventor, by adding at least one element in Y, Sc and at least one element in Si, C in zirconium-base amorphous alloy simultaneously, and ensure the content ratio of Y, Sc and Si in alloy, C, not only greatly reduce the preparation requirement of alloy, also improve over-all properties and the stability of the zirconium-base amorphous alloy obtained simultaneously
The object of the invention is to the restriction of zirconium-base amorphous alloy to working condition of customer service prior art, under the condition keeping good mechanical property, relax the requirement to material purity, melting vacuum tightness, melting atmosphere oxygen level, speed of cooling, there is provided a kind of and meet above zirconium-base amorphous alloy required and preparation method thereof, solve the above-mentioned problems in the prior art.
The invention provides a kind of zirconium-base amorphous alloy, wherein, the composed as follows of this zirconium-base amorphous alloy is stated shown in general formula:
(Zr
1-x-yTi
xHf
y)
a(Cu
mNi
n)
bAl
cM
dN
e
Wherein a, b, c, d, e are atomicity, 30≤a≤90,15≤b≤60,5≤c≤35,0.1≤d≤20,0.1≤e≤5, and a, b, c, d, e sum is 100, x, y, m, n represent the atomic fraction of Ti, Hf, Cu, Ni respectively, 0≤x≤0.2,0≤y≤0.05,0.2≤m/n≤5, M is selected from least one in Y, Sc, and N is selected from least one in Si, C;
With the cumulative volume of described zirconium-base amorphous alloy for benchmark, the volume fraction of described crystalline phases is 5 ~ 50%, and the volume fraction of Amorphous Phase is 50 ~ 95%.
Zirconium-base amorphous alloy of the present invention, is further characterized in that,
The atomicity of described a, b, c, d, e, wherein 50≤a≤75,20≤b≤55,5≤c≤20,0.1≤d≤10,0.1≤e≤2, and a, b, c, d, e sum is 100, described x, y, m, n represents the atomic fraction of Ti, Hf, Cu, Ni respectively, 0≤x≤0.15,0≤y≤0.03,0.4≤m/n≤4.5;
The volume fraction of described crystalline phases is 10 ~ 25%, and the volume fraction of Amorphous Phase is 75 ~ 90%.
Present invention also offers the preparation method of this zirconium-base amorphous alloy; under the method is included in protection of inert gas or under vacuum condition; zirconium-base amorphous alloy starting material are carried out melting and cooling forming; wherein; the starting material of described non-crystaline amorphous metal comprise Zr, Ti, Hf, Cu, Ni, Al, M, N, and the add-on of each material makes consisting of of the alloy of gained: (Zr
1-x-yti
xhf
y)
a(Cu
mni
n)
bal
cm
dn
e.
The preparation method of zirconium-base amorphous alloy of the present invention, is further characterized in that,
Described rare gas element is one or more in helium, neon, argon, krypton, xenon, radon gas body, and the purity of gas is not less than 94% of volume percent;
Described vacuum condition is below 1000Pa, represents with absolute pressure;
Described smelting temperature is 1000 ~ 3000 DEG C;
Described smelting time is 0.5 ~ 10 minute.
Preferably, described vacuum condition is less than 100Pa; Described smelting temperature is 1200 ~ 2700 DEG C; Described smelting time is 2 ~ 5 minutes.
Preferred, described vacuum condition is 0.1 ~ 50Pa.
Zirconium-base amorphous alloy of the present invention, by the atomic percentage conc of each component in adjustment zirconium-base amorphous alloy, and in zirconium-base amorphous alloy, add non-metallic element Y, Sc, the preparation requirement of this non-crystaline amorphous metal can be reduced, the more important thing is under the prerequisite keeping over-all properties not decline, greatly reduce the high request to material purity, allow to retain a certain amount of impurity element in starting material simultaneously.Therefore, by suitably adjusting the ratio of the non-metallic elements such as Si, C in non-crystaline amorphous metal, not only can not affect the over-all properties of zirconium-base amorphous alloy, the pressure of material cost during industrialized mass production can be reduced on the contrary, promote the paces of non-crystaline amorphous metal volume production.
The bulk zirconium-base amorphous alloy of critical size at more than 3mm can also be obtained by preparation method of the present invention, this zirconium-base amorphous alloy not only has excellent mechanical property, simultaneously lower to the content requirement of material purity and impurity element, allow the metallic impurity elements being less than or equal to 5% (atomic percent), and the nonmetallic impurity element being less than or equal to 1% (atomic percent) exists.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The invention provides a kind of zirconium-base amorphous alloy, wherein, the composed as follows of this zirconium-base amorphous alloy is stated shown in general formula:
(Zr
1-x-yTi
xHf
y)
a(Cu
mNi
n)
bAl
cM
dN
e
Wherein a, b, c, d, e are atomicity, 30≤a≤90,15≤b≤60,5≤c≤35,0.1≤d≤20,0.1≤e≤5, and a, b, c, d, e sum is 100, x, y, m, n represent the atomic fraction of Ti, Hf, Cu, Ni respectively, 0≤x≤0.2,0≤y≤0.05,0.2≤m/n≤5, M is selected from least one in Y, Sc, and N is selected from least one in Si, C.
With the cumulative volume of described zirconium-base amorphous alloy for benchmark, the volume fraction of described crystalline phases is 5 ~ 50%, and the volume fraction of Amorphous Phase is 50 ~ 95%.
Under preferable case, the atomicity of described a, b, c, d, e, wherein 50≤a≤75,20≤b≤55,5≤c≤20,0.1≤d≤10,0.1≤e≤2, and a, b, c, d, e sum is 100, described x, y, m, n represent the atomic fraction of Ti, Hf, Cu, Ni respectively, 0≤x≤0.15,0≤y≤0.03,0.4≤m/n≤4.5;
The volume fraction of described crystalline phases is 10 ~ 25%, and the volume fraction of Amorphous Phase is 75 ~ 90%.
Because suitability for industrialized production generally adopts master alloy that price is more cheap as raw material, thus can make in the zirconium-base amorphous alloy obtained containing some elementary metal impurities, as Mg, Ca, Co etc., and some non-metallic elements, as C, O, N, B, P etc., but for the present invention, the existence of a certain amount of impurity metallic elements can't affect that the present invention obtains the performance of zirconium-base amorphous alloy, as: with the total amount of affiliated zirconium-base amorphous alloy for benchmark, described zirconium-base amorphous alloy can be less than or equal to the metallic impurity elements of 5% containing atomic percent, atomic percent is less than or equal to the nonmetallic impurity element of 1%, when foreign matter content is stated in scope on the invention, on melting and the preparation not impact of zirconium-base amorphous alloy provided by the invention.
The present invention is selected from least one in Y, Sc as M, when N is selected from least one in Si, C.The over-all properties of zirconium-base amorphous alloy is more excellent.
As long as the purity for the preparation of the various raw materials of zirconium-base amorphous alloy of the present invention meets conventional requirement can be preferably mass percent more than 98%.
The preparation method of zirconium-base amorphous alloy of the present invention, can be achieved the different ratios of crystalline phases and Amorphous Phase in the described zirconium-base amorphous alloy of adjustment by the composition of the zirconium-base amorphous alloy described in controlling according to the condition that the method controlled cooling model of this area routine is shaping.The condition of described cooling forming comprises speed of cooling, pressure, mold material and mould thermal conductivity etc.Wherein, one of the key factor of crystalline phases and Amorphous Phase ratio control in zirconium-base amorphous alloy during speed of cooling, and the range of choice of the conditions such as pressure, mold material and mould thermal conductivity is wider, it coordinates chooser will guarantee to obtain suitable speed of cooling can meet described cooling forming condition.In known casting mode, the volume fraction of crystalline phases usually and speed of cooling be that reverse proportionality is just washed.According to the present invention, described speed of cooling can be selected within the scope of normal condition, as more than 10K/s, is preferably 10-10
4k/s.
The preparation method of zirconium-base amorphous alloy of the present invention, described rare gas element is one or more in helium, neon, argon, krypton, xenon, radon gas body, and the purity of gas is not less than 94% of volume percent;
Described vacuum condition is below 1000Pa, represents with absolute pressure;
Described smelting temperature is 1000 ~ 3000 DEG C;
Described smelting time is 0.5 ~ 10 minute.
Under preferable case, smelting time described in the present invention can 2 ~ 5 minutes.
The melting equipment adopted can be conventional melting equipment, such as vacuum arc melting furnace, vacuum induction furnace or vacuum resistance furnace.
The one-tenth sexuality of zirconium-base amorphous alloy provided by the invention is strong, and therefore, described cooling forming can adopt the pressure die casting forming method of the various routine in this area, the material such as stainless steel, copper alloy.Mold cools down can adopt the mode such as water-cooled, oil cooling.
Embodiment
Embodiment 1
Be that the various zirconium-base amorphous alloy starting material of mass ratio 99% drop in arc-melting furnaces by purity; arc-melting furnace is evacuated to 10Pa; then passing into purity is that the argon gas of percent by volume 99.9% is as shielding gas; at 1500 DEG C; melting 3 minutes, makes the abundant melting of zirconium-base amorphous alloy raw material.The kind of this zirconium-base amorphous alloy raw material and atomic percentage conc are the Zr of 50%, atomic percentage conc is the Ti of 2%, atomic percentage conc is the Cu of 15%, atomic percentage conc is the Ni of 10%, atomic percentage conc is the Al of 15%, atomic percentage conc is the Y of 4%, and atomic percentage conc is the Sc of 2%, and atomic percentage conc is the Si of 2%.
The sample of melting is casted into cooling forming in copper alloy die by the method for pressure die casting, namely obtains zirconium-base amorphous alloy (Zr
1-x-yti
xhf
y)
a(Cu
mni
n)
bal
cm
dn
e.
Embodiment 2
Be that the various zirconium-base amorphous alloy starting material of mass ratio 99% drop in arc-melting furnaces by purity, arc-melting furnace is evacuated to 10
-1pa, then pass into purity be the argon gas of percent by volume 99.9% as shielding gas, at 1650 DEG C, melting 3 minutes, makes the abundant melting of zirconium-base amorphous alloy raw material.The kind of this zirconium-base amorphous alloy raw material and atomic percentage conc are the Zr of 60%, atomic percentage conc is the Ti of 3%, atomic percentage conc is the Hf of 2%, atomic percentage conc is the Cu of 12.5%, and atomic percentage conc is the Ni of 7.5%, and atomic percentage conc is the Al of 5%, atomic percentage conc is the Y of 5%, atomic percentage conc is the Sc of 3%, and atomic percentage conc is the Si of 1.5%, and atomic percentage conc is the C of 0.5%.
The sample of melting is casted into cooling forming in copper alloy die by the method for pressure die casting, namely obtains zirconium-base amorphous alloy (Zr
1-x-yti
xhf
y)
a(Cu
mni
n)
bal
cm
dn
e.
Embodiment 3
Be that the various zirconium-base amorphous alloy starting material of mass ratio 99% drop in arc-melting furnaces by purity, arc-melting furnace is evacuated to 10
-1pa, then pass into purity be the argon gas of percent by volume 99.9% as shielding gas, at 1600 DEG C, melting 3 minutes, makes the abundant melting of zirconium-base amorphous alloy raw material.The kind of this zirconium-base amorphous alloy raw material and atomic percentage conc are the Zr of 60%, atomic percentage conc is the Ti of 1.5%, atomic percentage conc is the Hf of 0.5%, atomic percentage conc is the Cu of 10.5%, atomic percentage conc is the Ni of 9.5%, and atomic percentage conc is the Al of 8%, and atomic percentage conc is the Y of 0.5%, atomic percentage conc is the Sc of 1.2%, and atomic percentage conc is the Si of 0.3%.
The sample of melting is casted into cooling forming in copper alloy die by the method for pressure die casting, namely obtains zirconium-base amorphous alloy (Zr
1-x-yti
xhf
y)
a(Cu
mni
n)
bal
cm
dn
e.
Comparison example 1
According to preparation method's zirconium-base amorphous alloy of embodiment 1, unlike, the purity of zirconium-base amorphous alloy raw material is 99.8%.
Be that the various zirconium-base amorphous alloy starting material of mass ratio 99.8% drop in arc-melting furnaces by purity; arc-melting furnace is evacuated to 10Pa; then passing into purity is that the argon gas of percent by volume 99.9% is as shielding gas; at 1500 DEG C; melting 3 minutes, makes the abundant melting of zirconium-base amorphous alloy raw material.The kind of this zirconium-base amorphous alloy raw material and consumption to be atomic percentage conc be 50.9% Zr, atomic percentage conc is the Cu of 29.9%, and atomic percentage conc is the Ni of 7.4%, and atomic percentage conc is the Al of 9.8%, and atomic percentage conc is the Y of 2%.
Comparison example 2
Purity is weight percentage 99.7% various zirconium-base amorphous alloy starting material put in arc-melting furnace; arc-melting furnace is evacuated to 10Pa; then passing into volume percent is that the argon gas of 99.9% is as shielding gas; at 1800 DEG C; melting 3 minutes, makes the abundant melting of zirconium-base amorphous alloy raw material.The kind of this zirconium-base amorphous alloy raw material and consumption to be atomic percentage conc be 55% Zr, atomic percentage conc is the Ti of 2%, atomic percentage conc is the Cu of 16.5%, atomic percentage conc is the Ni of 13.5%, atomic percentage conc is the Al of 9.6%, atomic percentage conc is the Y of 0.4%, and atomic percentage conc is the Nb of 3%.
Detect three kinds of methods detect finally by metallographic microanalysis, bending strength test, oxygen level, detected result sees the following form:
As can be seen from table, the non-crystaline amorphous metal prepared according to proportioning of the present invention and method, can obtain the non-crystaline amorphous metal of excellent performance when low material purity, low preparation condition.The crystalline phases ratio control of the non-crystaline amorphous metal adopting the present invention to obtain is within 10-25%, and oxygen level, between 600-1200ppm, can obtain better mechanical property compared with the traditional zirconium-base amorphous alloy represented with comparative example.
Above-mentioned embodiment is an example of the present invention, is not used to limit enforcement of the present invention and interest field, and all equivalences made according to the content described in the present patent application scope of patent protection change and modify, and all should be included in the present patent application the scope of the claims.
Claims (6)
1. a zirconium-base amorphous alloy, wherein, the composed as follows of this zirconium-base amorphous alloy is stated shown in general formula:
(Zr
1-x-yTi
xHf
y)
a(Cu
mNi
n)
bAl
cM
dN
e
Wherein a, b, c, d, e are atomicity, 30≤a≤90,15≤b≤60,5≤c≤35,0.1≤d≤20,0.1≤e≤5, and a, b, c, d, e sum is 100, x, y, m, n represent the atomic fraction of Ti, Hf, Cu, Ni respectively, 0≤x≤0.2,0≤y≤0.05,0.2≤m/n≤5, M is selected from least one in Y, Sc, and N is selected from least one in Si, C;
With the cumulative volume of described zirconium-base amorphous alloy for benchmark, the volume fraction of described crystalline phases is 5 ~ 50%, and the volume fraction of Amorphous Phase is 50 ~ 95%.
2. zirconium-base amorphous alloy according to claim 1, is characterized in that, the atomicity of described a, b, c, d, e, wherein 50≤a≤75,20≤b≤55,5≤c≤20,0.1≤d≤10,0.1≤e≤2, and a, b, c, d, e sum is 100, described x, y, m, n represents the atomic fraction of Ti, Hf, Cu, Ni respectively, 0≤x≤0.15,0≤y≤0.03,0.4≤m/n≤4.5;
The volume fraction of described crystalline phases is 10 ~ 25%, and the volume fraction of Amorphous Phase is 75 ~ 90%.
3. the preparation method of zirconium-base amorphous alloy described in a claim 1; it is characterized in that; under the method is included in protection of inert gas or under vacuum condition; zirconium-base amorphous alloy starting material are carried out melting and cooling forming; wherein; the starting material of described non-crystaline amorphous metal comprise Zr, Ti, Hf, Cu, Ni, Al, M, N, and the add-on of each material makes consisting of of the alloy of gained:
(Zr
1-x-yTi
xHf
y)
a(Cu
mNi
n)
bAl
cM
dN
e。
4. the preparation method of zirconium-base amorphous alloy according to claim 3, is characterized in that, described rare gas element is one or more in helium, neon, argon, krypton, xenon, radon gas body, and the purity of gas is not less than 94% of volume percent;
Described vacuum condition is below 1000Pa, represents with absolute pressure;
Described smelting temperature is 1000 ~ 3000 DEG C;
Described smelting time is 0.5 ~ 10 minute.
5. the preparation method of zirconium-base amorphous alloy according to claim 3, is characterized in that, described vacuum condition is less than 100Pa; Described smelting temperature is 1200 ~ 2700 DEG C; Described smelting time is 2 ~ 5 minutes.
6. the preparation method of zirconium-base amorphous alloy according to claim 3, is characterized in that, described vacuum condition is 0.1 ~ 50Pa.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310410770.9A CN103484800B (en) | 2013-09-10 | 2013-09-10 | A kind of zirconium-base amorphous alloy and preparation method thereof |
| PCT/CN2014/084500 WO2015035845A1 (en) | 2013-09-10 | 2014-08-15 | Zirconium-based amorphous alloy and preparation method therefor |
| EP14843474.9A EP3045557B1 (en) | 2013-09-10 | 2014-08-15 | Zirconium-based amorphous alloy and preparation method therefor |
| US15/065,807 US20160186293A1 (en) | 2013-09-10 | 2016-03-09 | Zirconium-based amorphous alloy and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310410770.9A CN103484800B (en) | 2013-09-10 | 2013-09-10 | A kind of zirconium-base amorphous alloy and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103484800A CN103484800A (en) | 2014-01-01 |
| CN103484800B true CN103484800B (en) | 2015-12-09 |
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ID=49825387
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| Country | Link |
|---|---|
| US (1) | US20160186293A1 (en) |
| EP (1) | EP3045557B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9353428B2 (en) * | 2012-03-29 | 2016-05-31 | Washington State University | Zirconium based bulk metallic glasses with hafnium |
| CN103484800B (en) * | 2013-09-10 | 2015-12-09 | 黄利敏 | A kind of zirconium-base amorphous alloy and preparation method thereof |
| CN105132837B (en) * | 2015-08-27 | 2017-04-12 | 常州世竟液态金属有限公司 | Low-cost bulk amorphous alloy |
| CN105132834B (en) * | 2015-09-10 | 2017-08-25 | 深圳市锆安材料科技有限公司 | A kind of high intensity non-crystaline amorphous metal and preparation method thereof |
| CN105112817B (en) * | 2015-09-10 | 2017-03-29 | 深圳市锆安材料科技有限公司 | A kind of non-crystaline amorphous metal of wear-and corrosion-resistant and preparation method thereof |
| CN110106456B (en) * | 2018-01-19 | 2021-12-17 | 东莞市坚野材料科技有限公司 | Amorphous alloy stent and preparation method thereof |
| CN108193147B (en) * | 2018-02-07 | 2020-11-27 | 瑞声精密制造科技(常州)有限公司 | High-toughness zirconium-based amorphous alloy material and preparation method thereof |
| CN109548765B (en) * | 2019-01-04 | 2024-01-02 | 鄱阳县黑金刚钓具有限责任公司 | Fishhook and manufacturing method thereof |
| CN109786338B (en) * | 2019-01-21 | 2021-07-09 | 盘星新型合金材料(常州)有限公司 | Amorphous alloy flexible substrate |
| CN115637395A (en) * | 2022-09-19 | 2023-01-24 | 盘星新型合金材料(常州)有限公司 | High-hardness large-size zirconium-based amorphous alloy with plastic deformation and preparation method thereof |
| CN116005083B (en) * | 2023-03-23 | 2023-06-27 | 松诺盟科技有限公司 | Amorphous material for torque shaft, torque shaft and torque sensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351192A (en) * | 2000-11-01 | 2002-05-29 | 中国科学院金属研究所 | Zr-based amorphous alloy with high formation power |
| CN101003884A (en) * | 2007-01-10 | 2007-07-25 | 北京航空航天大学 | Zirconium based amorphous alloy |
| CN101012534A (en) * | 2007-02-01 | 2007-08-08 | 北京航空航天大学 | New type zirconium-based amorphous alloy |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6682611B2 (en) * | 2001-10-30 | 2004-01-27 | Liquid Metal Technologies, Inc. | Formation of Zr-based bulk metallic glasses from low purity materials by yttrium addition |
| KR100701027B1 (en) * | 2005-04-19 | 2007-03-29 | 연세대학교 산학협력단 | Monolithic Metallic Glasses With Enhanced Ductility |
| CN102041461B (en) * | 2009-10-22 | 2012-03-07 | 比亚迪股份有限公司 | Zr-based amorphous alloy and preparation method thereof |
| CN102041462B (en) * | 2009-10-26 | 2012-05-30 | 比亚迪股份有限公司 | Zirconium-based amorphous alloy and preparation method thereof |
| CN102051533A (en) * | 2009-10-29 | 2011-05-11 | 鸿富锦精密工业（深圳）有限公司 | Zirconium-based amorphous alloy, spectacle frame and manufacturing method thereof |
| CN102061429B (en) * | 2009-11-13 | 2012-11-21 | 比亚迪股份有限公司 | Zirconium base amorphous composite material and preparation method thereof |
| CN102534437A (en) * | 2011-12-15 | 2012-07-04 | 比亚迪股份有限公司 | Amorphous alloy and method for preparing same |
| CN103484800B (en) * | 2013-09-10 | 2015-12-09 | 黄利敏 | A kind of zirconium-base amorphous alloy and preparation method thereof |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351192A (en) * | 2000-11-01 | 2002-05-29 | 中国科学院金属研究所 | Zr-based amorphous alloy with high formation power |
| CN101003884A (en) * | 2007-01-10 | 2007-07-25 | 北京航空航天大学 | Zirconium based amorphous alloy |
| CN101012534A (en) * | 2007-02-01 | 2007-08-08 | 北京航空航天大学 | New type zirconium-based amorphous alloy |
Non-Patent Citations (1)
| Title |
|---|
| 锆基非晶合金的研究进展与应用;黄劲松 等;《中国有色金属学报》;20031231;第13卷(第6期);第1321-1332页 * |
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| Publication number | Publication date |
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| EP3045557A4 (en) | 2016-08-31 |
| EP3045557A1 (en) | 2016-07-20 |
| EP3045557B1 (en) | 2019-04-17 |
| WO2015035845A1 (en) | 2015-03-19 |
| US20160186293A1 (en) | 2016-06-30 |
| CN103484800A (en) | 2014-01-01 |
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