CN104419879B - A kind of zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region - Google Patents
A kind of zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region Download PDFInfo
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Abstract
The invention discloses a kind of zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region.Its alloying element percentage expression formula is ZraTibNicCudBeeAlfCrgSih, wherein 41≤a≤47,9≤b≤13,8≤c≤12,8≤d≤10,22≤e≤28,0≤f≤2,0≤g≤0.5,0≤h≤0.5, and be zero during f, g, h difference, a+b+c+d+e+f+g+h=100.The remarkable advantage of the present invention is: this system non-crystaline amorphous metal has preferable antioxygenic property: conventional zirconium-base amorphous alloy does not the most possess antioxygenic property or antioxygen property is very poor, and the non-crystaline amorphous metal of the present invention has fine antioxygenic property, it is incubated half an hour, almost without oxidation weight gain in the air of 400 DEG C；This system non-crystaline amorphous metal has wider supercooling liquid phase region, and supercooling liquid phase region scope is about 120 DEG C, has good heat ductile forming ability；The non-oxidizability of this series alloy, good thermoplastic forming ability improve the actual application value of non-crystaline amorphous metal, it is ensured that this Amorphous Alloy has broad application prospects in the field such as structural material, medical apparatus and instruments.
Description
Technical field
The present invention relates to the non-crystaline amorphous metal of a kind of wide supercooling liquid phase region with antioxygenic property, belong to non-crystaline amorphous metal green wood
Material field.
Background technology
There is not long range ordered structure as crystalline material in the atomic arrangement of non-crystaline amorphous metal, but in shortrange order long-range
Unordered, the most there is not the defects such as the crystal boundary in crystalline material, dislocation, thus non-crystaline amorphous metal has many excellent performances, as
High intensity, good decay resistance and high elastic limit, be acknowledged as most potential new structural material.Such as,
Compared with corresponding crystal alloy material, zirconium-base amorphous alloy has: (1) higher hot strength and lower elastic modelling quantity；
(2) in the case of fatigue limit is suitable, there is higher endurance stress level；(3) in certain strain rate and shaping temperature
Under degree, there is good Plastic Forming performance；(4) Newtonian fluid behavior is shown in supercooling liquid phase region so that it is have good
Forming property, can realize the duplication to minutiae；(5) there is below glass transition temperature preferable heat stability, have
The corrosion resistance that wider forming temperature is interval and excellent.Therefore, structural material, national defence, space flight and aviation, biologic medical,
The field such as electronics, chemical industry has broad application prospects.
Block amorphous alloy (bulk metallic glass) is a class new material, often has wider supercooled liquid phase sector width
△ Tx=Tx-Tg, in formula, Tx is crystallization temperature, and Tg is glass transformation temperature, in the critical cooling rate of Tg ~ Tx
Block amorphous alloy has superplasticity, as plastics, it can be carried out heat ductile forming, and block amorphous alloy is cooled to simultaneously
During below glass transformation temperature Tg, the feature of the high strength and high hardness of remote ultra-traditional metal material can be had again.But, pure zirconium is originally
The activity of body is the highest, easily reacts with oxygen, generates ZrO2Crystallization.And add the zirconium-base amorphous alloy tool of multiple alloying element
Have and cross cold-zone and the highest heat stability on a large scale.
Sun et al. is once with Zr60Al15Ni25Block amorphous alloy carries out oxidation experiment in the dry oxygen when 310 ~ 410 DEG C,
Its result shows that the oxidated layer thickness of this alloy can increase along with the rising of oxidizing temperature.Xie Xinxin et al. have studied
Zr55Cu30Al10Ni5Block amorphous alloy carries out high-temperature oxydation test under the air ambient when 300 ~ 500 DEG C, its experimental result
Showing, this alloy occurs in that obvious oxidative phenomena, prolongation over time at the very start in experiment, and oxidated layer thickness increases.
The most in general, the antioxygenic property of non-crystaline amorphous metal is poor, needs to carry out heat under vacuum or protective atmosphere
Process so that one can in atmosphere heat treatment and do not aoxidize, and the bulk amorphous alloy that other performances are basically unchanged
Alloy.
Summary of the invention
It is an object of the invention to provide a kind of zirconium-base amorphous alloy, designed by suitable composition, develop and there is antioxygen
Change and have the block amorphous alloy of wide supercooling liquid phase region, solve current non-crystaline amorphous metal in atmosphere or hot in non-protected atmosphere at
Manage oxidizable problem.
The principle of the present invention is: non-crystaline amorphous metal is when carrying out heat treatment, it usually needs in a vacuum or protective atmosphere condition
Under carry out, which increases the manufacturing cost of non-crystaline amorphous metal, limit its actual application, in order to improve the antioxygen of non-crystaline amorphous metal
The property changed, to increase the practical ranges of alloy, it is provided that a kind of Zr-Ti-Ni-Cu-Be-Al-Cr-Si block amorphous alloy, should
It is that amorphous has preferable antioxygenic property.
The present invention asks for the technical scheme of solution: the zirconium-base amorphous conjunction of a kind of wide supercooling liquid phase region with non-oxidizability
Gold, described alloying element percentage expression formula is ZraTibNicCudBeeAlfCrgSih, wherein 41≤a≤47,9≤b≤13,8≤
C≤12,8≤d≤10,22≤e≤28,0≤f≤2,0≤g≤0.5,0≤h≤0.5, and be zero during f, g, h difference, a+b+c+
d+e+f+g+h=100.This Amorphous Alloy has non-oxidizability, and has wide supercooling liquid phase region, supercooling liquid phase region model
Enclose is about 120 DEG C.
A kind of zirconium-base amorphous alloy with non-oxidizability and wide supercooling liquid phase region, described alloy use copper mold casting method or
Prepared by person's water quenching.
Wherein water quenching includes following preparation process:
Prepared by step 1, foundry alloy: by block simple metal Zr, Ti, Ni, Cu, Be, Al, Cr, Si by selected atomic component
Proportioning, in high-purity Ar protective atmosphere, non-consumable is smelted into uniform mother alloy ingot；
Prepared by step 2, non-crystaline amorphous metal: pulverized by mother alloy ingot and load quartz glass tube, be evacuated to 10-3Seal after Pa
Dress, is heated to above alloy melting point 200K in resistance furnace and is incubated 1h, be allowed to re-melting, mix homogeneously, finally carry out shrend, obtain
Obtain the block amorphous alloy of selected components.
Copper mold casting method includes following preparation process:
Step 1, the preparation of foundry alloy: by Zr, Ti, Ni, Cu, Be, Al, Cr, Si by the atomic percent in design composition,
Carrying out dispensing after changing into percentage by weight, the purity of various raw metals is all technical purity.First regulation smelting furnace vacuum
The vacuum of room is to 2*10-3Pa~5*10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1*105Pa~0.8*
105Pa, places into raw material and carries out melting.During foundry alloy melting, fusion process process need to be repeated 3 ~ 5 times；Melting mixing is all
Cool down after even, obtain mother alloy ingot；
Prepared by step 2, non-crystaline amorphous metal sample: use common metal mold casting method, mother alloy ingot weight step 1 prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt is sucked in water-cooled metal copper mold, obtain non-crystaline amorphous metal.
The present invention is compared with existing zirconium-base amorphous alloy, and its remarkable advantage is:
1, this system non-crystaline amorphous metal has preferable antioxygenic property: conventional zirconium-base amorphous alloy does not the most possess antioxygen
Change performance or antioxygen property is very poor, and the non-crystaline amorphous metal of the present invention has fine antioxygenic property, protects in the air of 400 DEG C
Warm half an hour, almost without oxidation weight gain；
2, this system non-crystaline amorphous metal has wider supercooling liquid phase region, and supercooling liquid phase region scope is about 120 DEG C, has good
Good heat ductile forming ability；
3, the non-oxidizability of this series alloy, good thermoplastic forming ability improve the actual application valency of non-crystaline amorphous metal
Value, it is ensured that this Amorphous Alloy has broad application prospects in the field such as structural material, medical apparatus and instruments.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
Embodiment 1. Zr44Ti10Ni10Cu10Be25Al1
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, aluminium block by the atom in design composition
Percentage ratio, carries out dispensing after changing into percentage by weight.The vacuum of regulation smelting furnace vacuum chamber is to 2*10-3Pa~5*10- 3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1*105Pa~0.8*105Pa, places into raw material melting.During melting
First put into dystectic metal Zr, Ti and Ni, form alloy cast ingot, add low-melting-point metal Cu, Be and carry out melting, form casting
Ingot, is eventually adding Cu and carries out melting, and fusion process repeats 3 ~ 5 times, after melting uniformly, obtains mother alloy ingot after cooling.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 80mm.Its glass transition temperature TgIt is 351 DEG C, crystallization temperature TgFor
470 DEG C, supercooling liquid phase region △ TxIt it is 119 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 2. Zr44Ti11Ni10Cu10Be24.5Cr0.5
Prepared by water quenching.
By block simple metal Zr, Ti, Cu, Be, Ni, Cr by selected atomic component proportioning, in high-purity Ar protective atmosphere
Non-consumable is smelted into uniform mother alloy ingot.First put into dystectic metal Zr, Ti, Cr and Ni during melting, form alloy cast
Ingot, adds low-melting-point metal Cu, Be and carries out melting, to reduce the loss on ignition of low-melting-point metal, it is ensured that alloying component accurate
Property.Fusion process need to be repeated 3 ~ 5 times.Mother alloy ingot is pulverized and loads quartz glass tube, pumping high vacuum (~ 10-3Pa) after
Encapsulation.In resistance furnace, it is heated to above alloy melting point 200K is incubated 1h, be allowed to re-melting, mix homogeneously, finally carry out shrend,
Obtain the block amorphous alloy of selected components.
The a diameter of 18mm of made bulk amorphous alloy, is about 30mm.Its glass transition temperature TgIt is 353 DEG C, crystallization temperature TxFor
471 DEG C, supercooling liquid phase region △ TxIt it is 118 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 3. Zr44Ti11Ni10Cu9.5Be25Si0.5
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, silico briquette by the atom in design composition
Percentage ratio, carries out dispensing after changing into percentage by weight, the purity of various raw metals is all technical purity.Regulation smelting furnace
The vacuum of vacuum chamber is to 2*10-3Pa~5*10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1*105Pa~
0.8*105Pa, places into raw material melting.First put into dystectic metal Zr, Ti, Si and Ni during melting, form alloy cast ingot, then
Adding low-melting-point metal Cu, Be and carry out melting, fusion process repeats 3 ~ 5 times, after melting uniformly, obtains foundry alloy casting after cooling
Ingot.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 75mm.Its glass transition temperature TgIt is 359 DEG C, crystallization temperature TxFor
474 DEG C, supercooling liquid phase region △ TxIt it is 115 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 4. Zr44Ti11Ni10Cu9.5Be24.5Cr0.5Si0.5
Prepared by water quenching.
By block simple metal Zr, Ti, Cu, Be, Ni, Cr, Si by selected atomic component proportioning, at high-purity Ar protective atmosphere
Middle non-consumable is smelted into uniform mother alloy ingot.First put into dystectic metal Zr, Ti, Cr and Ni during melting, form alloy
Ingot casting, adds low-melting-point metal Si, Cu, Be and carries out melting, to reduce the loss on ignition of low-melting-point metal, it is ensured that alloying component
Accuracy.Fusion process need to be repeated 3 ~ 5 times.Mother alloy ingot is pulverized and loads quartz glass tube, pumping high vacuum (~ 10- 3Pa) post package.In resistance furnace, it is heated to above alloy melting point 200K is incubated 1h, be allowed to re-melting, mix homogeneously, the most laggard
Row shrend, it is thus achieved that the block amorphous alloy of selected components.
The a diameter of 18mm of made bulk amorphous alloy, is about 30mm.Its glass transition temperature TgIt is 356 DEG C, crystallization temperature TxFor
478 DEG C, supercooling liquid phase region △ TxIt it is 122 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 5. Zr44Ti10Ni10Cu9.5Be24.5Cr0.5Si0.5Al1
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, silico briquette, chromium block, aluminium block by being designed to
Atomic percent in Fen, carries out dispensing after changing into percentage by weight, the purity of various raw metals is all technical purity.
The vacuum of regulation smelting furnace vacuum chamber is to 2*10-3Pa~5*10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber extremely
0.1*105Pa~0.8*105Pa, places into raw material melting.Dystectic metal Zr, Ti, Si, Cr and Ni, shape is first put into during melting
Becoming alloy cast ingot, add low-melting-point metal Cu, Be, Al and carry out melting, fusion process repeats 3 ~ 5 times, after melting uniformly, and cooling
After obtain mother alloy ingot.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 82mm.Its glass transition temperature TgIt is 354 DEG C, crystallization temperature TxFor
472 DEG C, supercooling liquid phase region △ TxIt it is 118 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 6:Zr44Ti9Ni10Cu10Be25Al2
Prepared by water quenching.
By block simple metal Zr, Ti, Cu, Be, Ni, Al by selected atomic component proportioning, in high-purity Ar protective atmosphere
Non-consumable is smelted into uniform mother alloy ingot.First put into dystectic metal Zr, Ti and Ni during melting, form alloy cast ingot,
Add low-melting-point metal Al, Cu, Be and carry out melting, to reduce the loss on ignition of low-melting-point metal, it is ensured that alloying component accurate
Property.Fusion process need to be repeated 3 ~ 5 times.Mother alloy ingot is pulverized and loads quartz glass tube, pumping high vacuum (~ 10-3Pa) after
Encapsulation.In resistance furnace, it is heated to above alloy melting point 200K is incubated 1h, be allowed to re-melting, mix homogeneously, finally carry out shrend,
Obtain the block amorphous alloy of selected components.
The a diameter of 18mm of made bulk amorphous alloy, is about 30mm.Its glass transition temperature TgIt is 354 DEG C, crystallization temperature TxFor
473 DEG C, supercooling liquid phase region △ TxIt it is 119 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 7:Zr44Ti9Ni10Cu9.5Be24.5Cr0.5Si0.5Al2
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, silico briquette, chromium block, aluminium block by being designed to
Atomic percent in Fen, carries out dispensing after changing into percentage by weight, the purity of various raw metals is all technical purity.
The vacuum of regulation smelting furnace vacuum chamber is to 2*10-3Pa~5*10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber extremely
0.1*105Pa~0.8*105Pa, places into raw material melting.Dystectic metal Zr, Ti, Si, Cr and Ni, shape is first put into during melting
Becoming alloy cast ingot, add low-melting-point metal Cu, Be, Al and carry out melting, fusion process repeats 3 ~ 5 times, after melting uniformly, and cooling
After obtain mother alloy ingot.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 77mm.Its glass transition temperature TgIt is 353 DEG C, crystallization temperature TxFor
472 DEG C, supercooling liquid phase region △ TxIt it is 119 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 8:Zr44Ti9Ni10Cu9.5Be25Si0.5Al2
Prepared by water quenching.
By block simple metal Zr, Ti, Cu, Be, Ni, Si, Al by selected atomic component proportioning, at high-purity Ar protective atmosphere
Middle non-consumable is smelted into uniform mother alloy ingot.First put into dystectic metal Zr, Ti, Si and Ni during melting, form alloy
Ingot casting, adds low-melting-point metal Cu, Be, Al and carries out melting, to reduce the loss on ignition of low-melting-point metal, it is ensured that alloying component
Accuracy.Fusion process need to be repeated 3 ~ 5 times.Mother alloy ingot is pulverized and loads quartz glass tube, pumping high vacuum (~ 10- 3Pa) post package.In resistance furnace, it is heated to above alloy melting point 200K is incubated 1h, be allowed to re-melting, mix homogeneously, the most laggard
Row shrend, it is thus achieved that the block amorphous alloy of selected components.
The a diameter of 18mm of made bulk amorphous alloy, is about 30mm.Its glass transition temperature TgIt is 357 DEG C, crystallization temperature TxFor
474 DEG C, supercooling liquid phase region △ TxIt it is 117 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 9:Zr44Ti9Ni10Cu10Be24.5Cr0.5Al2
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, chromium block, aluminium block by design composition
Atomic percent, carries out dispensing after changing into percentage by weight, the purity of various raw metals is all technical purity.Regulation smelting
The vacuum of furnace vacuum chamber is to 2*10-3Pa~5*10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1*105Pa
~0.8*105Pa, places into raw material melting.First put into dystectic metal Zr, Ti, Cr and Ni during melting, form alloy cast ingot,
Adding low-melting-point metal Cu, Be, Al melting, fusion process repeats 3 ~ 5 times, after melting uniformly, obtains foundry alloy casting after cooling
Ingot.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 75mm.Its glass transition temperature TgIt is 359 DEG C, crystallization temperature TxFor
474 DEG C, supercooling liquid phase region △ TxIt it is 115 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 10. Zr41Ti12Ni11Cu10Be25Al1
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, aluminium block by the atom in design composition
Percentage ratio, carries out dispensing after changing into percentage by weight.The vacuum of regulation smelting furnace vacuum chamber is to 2*10-3Pa~5*10- 3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1*105Pa~0.8*105Pa, places into raw material melting.During melting
First put into dystectic metal Zr, Ti and Ni, form alloy cast ingot, add low-melting-point metal Cu, Be and carry out melting, form casting
Ingot, is eventually adding Cu and carries out melting, and fusion process repeats 3 ~ 5 times, after melting uniformly, obtains mother alloy ingot after cooling.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 80mm.Its glass transition temperature TgIt is 351 DEG C, crystallization temperature TgFor
470 DEG C, supercooling liquid phase region △ TxIt it is 119 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 11.Zr47Ti9Ni10Cu9Be24.5Cr0.5
Prepared by water quenching.
By block simple metal Zr, Ti, Cu, Be, Ni, Cr by selected atomic component proportioning, in high-purity Ar protective atmosphere
Non-consumable is smelted into uniform mother alloy ingot.First put into dystectic metal Zr, Ti, Cr and Ni during melting, form alloy cast
Ingot, adds low-melting-point metal Cu, Be and carries out melting, to reduce the loss on ignition of low-melting-point metal, it is ensured that alloying component accurate
Property.Fusion process need to be repeated 3 ~ 5 times.Mother alloy ingot is pulverized and loads quartz glass tube, pumping high vacuum (~ 10-3Pa) after
Encapsulation.In resistance furnace, it is heated to above alloy melting point 200K is incubated 1h, be allowed to re-melting, mix homogeneously, finally carry out shrend,
Obtain the block amorphous alloy of selected components.
The a diameter of 18mm of made bulk amorphous alloy, is about 30mm.Its glass transition temperature TgIt is 353 DEG C, crystallization temperature TxFor
471 DEG C, supercooling liquid phase region △ TxIt it is 118 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 12.Zr44Ti11Ni12Cu7.5Be25Si0.5
Prepared by copper mold casting method.
Step 1: the preparation of foundry alloy.By zirconium block, titanium block, copper ingot, beryllium block, nickel block, silico briquette by the atom in design composition
Percentage ratio, carries out dispensing after changing into percentage by weight, the purity of various raw metals is all technical purity.Regulation smelting furnace
The vacuum of vacuum chamber is to 2*10-3Pa~5*10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1*105Pa~
0.8*105Pa, places into raw material melting.First put into dystectic metal Zr, Ti, Si and Ni during melting, form alloy cast ingot, then
Adding low-melting-point metal Cu, Be and carry out melting, fusion process repeats 3 ~ 5 times, after melting uniformly, obtains foundry alloy casting after cooling
Ingot.
Step 2: prepared by non-crystaline amorphous metal sample: use common metal mold casting method, the mother alloy ingot weight that step 1 is prepared
New fusing, utilizes the absorbing and casting device in electric arc furnace, mother alloy melt sucks in inert gas shielding atmosphere water-cooled metal copper
In mould, obtain non-crystaline amorphous metal.
The a diameter of 16mm of made bulk amorphous alloy, is about 75mm.Its glass transition temperature TgIt is 359 DEG C, crystallization temperature TxFor
474 DEG C, supercooling liquid phase region △ TxIt it is 115 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Embodiment 13:Zr44Ti9Ni8Cu9Be28Al2
Prepared by water quenching.
By block simple metal Zr, Ti, Cu, Be, Ni, Al by selected atomic component proportioning, in high-purity Ar protective atmosphere
Non-consumable is smelted into uniform mother alloy ingot.First put into dystectic metal Zr, Ti and Ni during melting, form alloy cast ingot,
Add low-melting-point metal Al, Cu, Be and carry out melting, to reduce the loss on ignition of low-melting-point metal, it is ensured that alloying component accurate
Property.Fusion process need to be repeated 3 ~ 5 times.Mother alloy ingot is pulverized and loads quartz glass tube, pumping high vacuum (~ 10-3Pa) after
Encapsulation.In resistance furnace, it is heated to above alloy melting point 200K is incubated 1h, be allowed to re-melting, mix homogeneously, finally carry out shrend,
Obtain the block amorphous alloy of selected components.
The a diameter of 18mm of made bulk amorphous alloy, is about 30mm.Its glass transition temperature TgIt is 354 DEG C, crystallization temperature TxFor
473 DEG C, supercooling liquid phase region △ TxIt it is 119 DEG C.And it is incubated half an hour in the air of 400 DEG C, almost without oxidation weight gain, embody
Well antioxygenic property.
Claims (4)
1. a zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region, it is characterised in that described alloying element hundred
Proportion by subtraction expression formula is: ZraTibNicCudBeeAlfCrgSih, wherein 41≤a≤47,9≤b≤13,8≤c≤12,8≤d≤10,
22≤e≤28,0≤f≤2,0≤g≤0.5,0≤h≤0.5, and be zero during f, g, h difference, a+b+c+d+e+f+g+h=100.
The zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region the most according to claim 1, its feature exists
Copper mold casting method or water quenching is used to prepare in described alloy.
The zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region the most according to claim 2, its feature exists
Following preparation process is included in described water quenching:
Step 1: prepared by foundry alloy, by block simple metal Zr, Ti, Ni, Cu, Be, Al, Cr, Si by selected atomic component proportioning,
In high-purity Ar protective atmosphere, non-consumable is smelted into uniform mother alloy ingot；
Step 2: prepared by non-crystaline amorphous metal, pulverizes mother alloy ingot and loads quartz glass tube, be evacuated to 10-3Pa post package,
Resistance furnace is heated to above alloy melting point 200K and is incubated 1h, be allowed to re-melting, mix homogeneously, finally carry out shrend, it is thus achieved that choosing
Determine the block amorphous alloy of composition.
The zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region the most according to claim 2, its feature exists
Following preparation process is included in copper mold casting method:
Step 1, the preparation of foundry alloy: by Zr, Ti, Ni, Cu, Be, Al, Cr, Si by the atomic percent in design composition, convert
Carrying out dispensing after becoming percentage by weight, the purity of various raw metals is all technical purity, first regulates smelting furnace vacuum chamber
Vacuum is to 2 × 10-3Pa～5 × 10-3Pa, then fills high-purity argon gas and makes the vacuum of vacuum chamber to 0.1 × 105Pa～0.8 ×
105Pa, places into raw material and carries out melting；Cool down after melting mix homogeneously, obtain mother alloy ingot；
Step 2, prepared by non-crystaline amorphous metal sample: use common metal mold casting method, is again melted by the mother alloy ingot that step 1 prepares
Change, utilize the absorbing and casting device in electric arc furnace, mother alloy melt is sucked in water-cooled metal copper mold, obtain non-crystaline amorphous metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310405102.7A CN104419879B (en) | 2013-09-06 | 2013-09-06 | A kind of zirconium-base amorphous alloy with antioxygenic property and wide supercooling liquid phase region |
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