CN1151308C - Multicomponent titanium-base alloy to form amorphous structure - Google Patents
Multicomponent titanium-base alloy to form amorphous structure Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 102
- 239000010936 titanium Substances 0.000 claims abstract description 128
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052796 boron Inorganic materials 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 238000005275 alloying Methods 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 abstract description 76
- 239000000463 material Substances 0.000 abstract description 37
- 229910052726 zirconium Inorganic materials 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 238000010671 solid-state reaction Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 4
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- 239000010949 copper Substances 0.000 description 104
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- 239000000203 mixture Substances 0.000 description 26
- 239000010955 niobium Substances 0.000 description 25
- 238000002441 X-ray diffraction Methods 0.000 description 24
- 239000011135 tin Substances 0.000 description 23
- 239000012071 phase Substances 0.000 description 20
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 14
- 150000002739 metals Chemical class 0.000 description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 13
- 229910052752 metalloid Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002076 thermal analysis method Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000013526 supercooled liquid Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000000048 melt cooling Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000000304 warm extrusion Methods 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910004353 Ti-Cu Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910004688 Ti-V Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 229910010968 Ti—V Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 238000012790 confirmation Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a multi-component titanium base alloy which can form an amorphous structure. The alloy comprises the components according to the expression: TiaMb(CuxNi<1-x>)cRdZe(a, b, c, d, and e stand for atomic percentage, and x is an atom fraction), wherein M is at least one of the elements of Mg, Ca, Mn, Nb, Fe, V, Mo and Zr, R is at least one of the elements of Al, Ag, Co, Fe, Pd and Zn, and Z is at least one element of B, Ge, Si, C and Sn; a is from 37 to 77%, b is from 0 to 27%, c is from 20 to 50%, d is from 0 to 17%, and e is from 1 to 15%; the total percentage of a, b, c, d and e is 100%, and x is from 0.35 to 0.75. According to the alloying components, an admixture prepared from elemental powder is used as starting materials, and the starting materials are treated by mechanical grinding and alloying, and are treated in a solid state reaction so that powder in an amorphous structure is formed; the volume percentage of an amorphous phase is not less than 50%. According to the alloying component, element block materials are used as starting materials, and the starting materials are smelted into a master alloy ingot; after the master alloy ingot is treated by mechanical crushing, powder in an amorphous structure is formed by mechanically grinding the debris of the master alloy ingot, and the volume percentage of an amorphous phase is not less than 50%.
Description
Technical field:
The present invention relates to the multicomponent titanium base alloy that a class can form amorphous structure.
Background technology:
Compare with conventional polycrystalline metal material, the primary structure of amorphous alloy (also claiming metallic glass) is characterized as the degree of order that atomic arrangement does not have long periodicity, does not also have crystal boundary.Therefore, has excellent performance such as high strength, corrosion-resistant, isotropy.Be with a wide range of applications in fields such as automobile, aircraft, micromachine, microelectronics, sports goods, precision instrument, burglary-resisting installation, energy transformation, medical materials.At present, the preparation method of amorphous alloy mainly comprises: methods such as melt supercooled, sputtering sedimentation, electrochemical deposition, gas ultrasonic atomizatio, ion beam irradiation, multilayer film diffusion annealing, mechanical mill.Because be subjected to the restriction of alloy intrinsic amorphous formation ability, obtainable amorphous metallic material great majority are confined to forms such as powder, strip, filament, film.The alloy that minority intrinsic amorphous formation ability is stronger, the critical cooling rate that is formed amorphous structure by liquid cooled can be lower than 500 ℃/second, can utilize the method for melt casting directly to form block materials or the part of thickness in the millimeter magnitude.
Amorphous alloy is to be in metastable material, can be transformed into the material (being referred to as crystallization change) of crystalline structure under the effect of external environments such as temperature, pressure, magnetic field, and this will be attended by the variation of alloy property.The intrinsic amorphous formation ability of alloy and thermostability directly depend on the chemical ingredients of alloy.Usually, the diversification of alloying constituent can improve (promptly being made up of multiple alloying element) the intrinsic amorphous formation ability and the thermostability of alloy.The key that forms amorphous structure by alloy melt cooling is that melt undercooling to the glass transformation temperature of alloy (is expressed as T
g) below, avoid crystallization to take place, freeze to become solid material.Some amorphous alloy is before crystallization change takes place in heating, has thermostability preferably, form more stable supercooled liquid, show as and when heat is analyzed, can be observed tangible glass transition and (change supercooled liquid into by amorphous solid, usually be attended by the sudden change of viscosity and specific heat), the supercooled liquid temperature range that can form broad (is expressed as Δ T
x, Δ T
xBe defined as the starting temperature T that crystallization change takes place amorphous alloy in continuous heat-processed
xWith glass transformation temperature T
gDifference, i.e. Δ T
x=T
x-T
g).In this temperature range, the anxious brush of the viscosity of amorphous alloy descends, and can show superplasticity, and this machine-shaping for amorphous alloy provides chance.Utilize this characteristic can realize nearly clean shape processing, amorphous alloy can be made into complex-shaped component, perhaps utilize powder metallurgy technology such as hot pressing, hot isostatic pressing, warm extrusion go out, sinter forging to be consolidated into block materials amorphous alloy powder or strip.Have now found that nearly tens of kinds can form amorphous alloy system and have These characteristics, Δ T
xValue can surpass more than 30 ℃, even greater than 100 ℃, as Mg-Ln-TM, Ln-Al-TM, Zr-Al-TM, Zr-(Ti, Nb, Pd)-and Al-TM, Zr-Ti-TM-Be, Fe-(Al, Ga)-(P, C, B, Si), Co-Cr-(Al, Ga)-(P, C, B, Si), Pd-Cu-Ni-P, Pd-Ni-Fe-P, (Fe, Co, Ni)-(Zr, Nb, Ta)-B, Fe-Co-(Zr, Nb)-(Mo, W)-B, Co-Fe-(Zr, Nb, Ta)-B alloy systems such as (Ln are a lanthanide series metal, and TM is a magnesium-yttrium-transition metal).
Compare with iron-based, zirconium base, palladium base amorphous alloy, titanium-based amorphous attitude alloy has low density, high strength, corrosion resistant characteristics.The density of principal element titanium is 4.5 gram per centimeters
3, fusing point is that 1668 ℃, thermal conductivity are that 0.036 card/cps degree, linear expansivity are 9.0 * 10
-6℃
-1The non-crystalline state Ti that adopts the melt supercooled method to form
50Cu
25Ni
25The tensile strength of alloy can reach 1800MPa, is 2 times of commercial titanium alloy Ti-6Al-4V, Ti-13V-11Cr-3Al and Ti-2Al-11.5V-2Sn-11.3Zr (Transage 129) 1.5 times.Have now found that, can form amorphous structure at some composition ranges of binary alloys such as Ti-Be, Ti-Cu, Ti-Ni, Ti-Mn, Ti-Si, Ti-V, Ti-Zr.Based on these alloys,, enlarge its range of application by adding the formation ability and the thermostability of the titanium-based amorphous attitude alloy of alloying element diversification will further the raising.
The technology contents of invention:
The invention provides the multicomponent titanium base alloy that a class can form amorphous structure, the expression formula of alloying constituent is:
(1)Ti
aM
b(Cu
xNi
1-x)
cZ
e，
A, b, c, e are atomic percent, x is an atomic fraction.
M is element M g, and Z is at least a element among element B, Ge, Si, C, the Sn.
a＝37～77％，b＝0.5～27％，c＝20～50％，e＝1～15％，a+b+c+e＝100％。x＝0.35～0.75。
(2)Ti
aM
b(Cu
xNi
1-x)
cZ
e，
A, b, c, e are atomic percent, x is an atomic fraction.
M is at least a element among element M g, Ca, Mn, Nb, Fe, V, Mo, the Zr, and Z is at least a in element S n or Sn and B, the Si element.
(3)a＝37～77％，b＝0.5～27％，c＝20～50％，e＝1～15％，a+b+c+e＝100％。x＝0.35～0.75。Ti
a(Cu
xNi
1-x)
cR
dZ
e，
A, c, d, e are atomic percent, x is an atomic fraction.
R is an element al,
Z is at least a element among element B, Ge, Si, C, the Sn.
a＝37～77％，c＝20～50％，d＝0.5～17％，e＝1～15％，a+c+d+e＝100％。
x＝0.35～0.75。
(4)Ti
a(Cu
xNi
1-x)
cR
dZ
e，
A, c, d, e are atomic percent, x is an atomic fraction.
R is at least a element among element al, Ag, Co, Fe, Pd, the Zn,
Z is at least a in element S n or Sn and B, the Si element.
a＝37～77％，c＝20～50％，d＝0.5～17％，e＝1～15％，a+c+d+e＝100％。x＝0.35～0.75。
(5)Ti
aM
b(Cu
xNi
1-x)
cR
dZ
e，
A, b, c, d, e are atomic percent, x is an atomic fraction.
M is element M g, and R is an element al,
Z is at least a element among element B, Ge, Si, C, the Sn.
a＝37～77％，b＝0.5～27％，c＝20～50％，d＝0.5～17％，e＝1～15％，a+b+c+d+e＝100％。x＝0.35～0.75。
(6)Ti
aM
b(Cu
xNi
1-x)
cR
dZ
e，
A, b, c, d, e are atomic percent, x is an atomic fraction.
M is at least a element among element M g, Ca, Mn, Nb, Fe, V, Mo, the Zr, and R is at least a element among element al, Ag, Co, Fe, Pd, the Zn,
Z is at least a in element S n or Sn and B, the Si element.
a＝37～77％，b＝0.5～27％，c＝20～50％，d＝0.5～17％，e＝1～15％，a+b+c+d+e＝100％。x＝0.35～0.75。
In the above-mentioned alloy, a, b, e preferably are chosen as, a=37～70%; B=0.5～20%, e=1～12%.
In the preparation method of many amorphous alloys, mechanical grinding method has following characteristics: (1) forms the alloy component range broad of amorphous structure, and, be confined to the composition range of narrower close alloy eutectic point usually by the amorphous alloy that the melt cooling forms; (2) can make fusing point differ alloy big, the not molten alloying element that mixes of liquid phase forms complicated component by solid state reaction; (3) technology of preparing is simple, is easy to industrialization, and powder output can reach feather weight, satisfies practicability demand widely.The amorphous alloy powder of method acquisition can be prepared into block materials or component by the various powders metallurgical technology according to demand thus.
The present invention also provides the preparation method of above-mentioned amorphous alloy, that is:
According to the given alloying constituent of expression formula, be parent material with commercially available element powders miscellany, through the mechanical mill alloying, form the powder of amorphous structure by solid state reaction, the percent by volume of amorphous phase is no less than 50%.The percent by volume of amorphous phase can be analyzed the amorphous phase crystallization change rejected heat that obtains by X-ray diffraction spectrum, electron microscope observation and differential scanning calorimetric (DSC) and estimate.
Perhaps, according to the given alloying constituent of expression formula, be parent material with the element block materials, form master alloy ingot through presmelting, master alloy ingot through mechanical mill, can form the powder of amorphous structure through the chip after the Mechanical Crushing, and the percent by volume of amorphous phase is no less than 50%.The percent by volume of amorphous phase can be analyzed the amorphous phase crystallization change rejected heat that obtains by X-ray diffraction spectrum, electron microscope observation and differential scanning calorimetric (DSC) and estimate.
In the mechanical mill process, for fear of the cold welding of powder or alloy chip, caking, bonding on the ball milling instrument, can add hydrocarbon polymers such as small amount of methanol, ethanol, stearic acid, vacuum grease as process control agent, the structure of grinding final product is not had influence.
In the titanium-based amorphous attitude alloy provided by the invention, some alloy has very strong amorphous formation ability and good thermostability, before crystallization change takes place in heating, forms more stable supercooled liquid, show tangible glass transition, the supercooled liquid temperature range of formation is above 50 ℃.This machine-shaping for amorphous alloy provides chance.Utilize this characteristic can realize nearly clean shape processing, amorphous powdered alloy is made into complex-shaped component, perhaps amorphous powdered alloy is utilized powder metallurgy technology such as hot pressing, hot isostatic pressing, warm extrusion go out, sinter forging to be consolidated into block materials such as plate, rod.
Description of drawings:
Fig. 1 composes for the X-ray diffraction of seven kinds of powdered alloys that mechanical mill forms,, the confirmation alloy is an amorphous structure.
A) Ti wherein
45Mg
5Cu
20Ni
24Si
4B
2(embodiment 1),
B) Ti
64V
10Fe
1Cu
7Ni
12Si
4B
2(embodiment 3),
C) Ti
50Cu
16Ni
20Al
8Si
4B
2(embodiment 5),
D) Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1(embodiment 7),
E) Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2(embodiment 9),
F) Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2(embodiment 11),
G) Ti
45Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2(embodiment 13)
Fig. 2 is the thermal analysis curve (heating rate is 40K/min) of seven kinds of powdered alloys of mechanical mill formation.
A) Ti wherein
45Mg
5Cu
20Ni
24Si
4B
2(embodiment 1),
B) Ti
64V
10Fe
1Cu
7Ni
12SiB
2(embodiment 3),
C) Ti
50Cu
16Ni
20Al
8Si
4B
2(embodiment 5),
D) Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1(embodiment 7),
E) Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2(embodiment 9),
F) Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2(embodiment 11),
G) Ti
5Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2(embodiment 13)
Embodiment:
Embodiment 1 Ti
45Mg
5Cu
20Ni
24Si
4B
2Alloy (alloying constituent is an atomic percent, at.%, down together).
As parent material, element powders purity all is higher than 99.5% (weight percent, wt.% descend together) with commercial metals element titanium, magnesium, copper, nickel by powder and metalloid element silicon, boron powder, and granularity is-200 or-325 orders, and being mixed with nominal composition is Ti
45Mg
5Cu
20Ni
24Si
4B
2Powder mixture.Powder mixture and GCr15 steel ball fill in the quenching stainless steel jar mill under high-purity Ar gas (99.99%) atmosphere than 5: 1 by ball and weight of material.Airtight ball grinder is installed on the SPEX 8000 high energy vibration formula ball mills grinds.Powder mixture turns out to be amorphous structure through X-ray diffraction after mechanical mill in 48 hours, promptly form amorphous Ti
45Mg
5Cu
20Ni
24Si
4B
2Alloy, amorphous volume percentage ratio is not less than 50%.The granularity of powder is about 20～100 microns.The heat analysis of ball-milled powder (differential scanning calorimeter, DSC, down together) curve can observe because the thermopositive reaction that heat absorption phenomenon that glass transition causes and crystallization cause.Ti through mechanical mill in 48 hours formation
45Mg
5Cu
20Ni
24Si
4B
2The X-ray diffraction spectrum and the hot analytical results of powdered alloy sample are seen Fig. 1 (a) and Fig. 2 (a) respectively.Ti
45Mg
5Cu
20Ni
24Si
4B
2The constitutional features of amorphous powdered alloy (amorphous, crystal or amorphous+crystal) and hot analytical results, i.e. glass transformation temperature (T
g), crystallization starting temperature (T
x) and supercooled liquid temperature province width (Δ T
x) list in table 1.
Embodiment 2 Ti
40Mn
10Cu
18Ni
26Si
4B
2Alloy.
As parent material, element powders purity all is higher than 99.5% with commercial metals element titanium, manganese, copper, nickel by powder and metalloid element silicon, boron powder, and granularity is-200 or-325 orders, and being mixed with nominal composition is Ti
40Mn
10Cu
18Ni
26Si
4B
2Powder mixture.The mechanical mill process is identical with embodiment 1.Confirm that through X-ray diffraction the element powders miscellany of ball milling after 48 hours is typical amorphous structure substantially, promptly form amorphous Ti
40Mn
10Cu
18Ni
26Si
4B
2Alloy.The granularity of powder is about 20～100 microns.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
Embodiment 3 Ti
64V
10Fe
1Cu
7Ni
12Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, vanadium, iron, copper, nickel and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
64V
10Fe
1Cu
7Ni
12Si
4B
2The nominal composition alloyage after, under high-purity Ar gas (99.999%) atmosphere arc melting become weight about 50 the gram mother alloy button ingot.Master alloy ingot is through the parent material of the chip after the Mechanical Crushing as follow-up mechanical mill.Mother alloy chip and GCr15 steel ball are filled in the quenching stainless steel jar mill under high-purity Ar gas (99.99%) atmosphere than 5: 1 by ball and weight of material.Airtight ball grinder is installed on the SPEX 8000 high energy vibration formula ball mills grinds.Powder mixture confirms that through X-ray diffraction parent material has changed amorphous structure into after mechanical mill in 32 hours, promptly form amorphous Ti
654V
10Fe
1Cu
7Ni
12Si
4B
2Alloy.The granularity of powder is about 20～100 microns.Do not observe the heat absorption phenomenon that causes owing to glass transition on the thermal analysis curve of ball-milled powder, but still the thermopositive reaction that crystallization causes occurs, further confirmed the non-crystalline state character of powder.Ti through mechanical mill in 32 hours formation
64V
10Fe
1Cu
7Ni
12Si
4B
2The X-ray diffraction spectrum and the hot analytical results of powdered alloy are seen Fig. 1 (b) and Fig. 2 (b) respectively.
Ti
64V
10Fe
1Cu
7Ni
12Si
4B
2The constitutional features of amorphous powdered alloy and hot analytical results are listed in table 1.
Embodiment 4 Ti
55Zr
5Fe
2Cu
13Ni
19Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, zirconium, iron, copper, nickel etc. and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
55Zr
5Fe
2Cu
13Ni
19Si
4B
2The nominal composition alloyage after, the preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The X-ray diffraction of ball milling powder after 48 hours confirms that powdered alloy changes amorphous structure into, promptly forms amorphous Ti
55Zr
5Fe
2Cu
13Ni
19Si
4B
2Alloy.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can be observed because the thermopositive reaction that heat absorption phenomenon that glass transition causes and crystallization cause.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
Embodiment 5 Ti
50Cu
16Ni
20Al
8Si
4B
2Alloy
With commercial metals element titanium, copper, nickel, aluminium powder form and metalloid element silicon, boron powder is parent material, and element powders purity all is higher than 99.5%, and granularity is-200 or-325 orders, and being mixed with nominal composition is Ti
50Cu
16Ni
20Al
8Si
4B
2Powder mixture, the mechanical mill process of powder is identical with embodiment 1.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction.Promptly form amorphous Ti
50Cu
16Ni
20Al
8Si
4B
2Alloy.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can observe because the thermopositive reaction that heat absorption phenomenon that glass transition causes and crystallization cause.Ti through mechanical mill in 48 hours formation
50Cu
16Ni
20Al
8Si
4B
2The X-ray diffraction spectrum and the hot analytical results of powdered alloy are seen Fig. 1 (c) and Fig. 2 (c) respectively.Ti
50Cu
16Ni
20Al
8Si
4B
2The constitutional features of amorphous powdered alloy and hot analytical results are listed in table 1.
Embodiment 6 Ti
70Cu
9Ni
13Co
2Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, copper, nickel, cobalt and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
70Cu
9Ni
13Co
2Si
4B
2The nominal composition alloyage after, the preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powdered alloy of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
70Cu
9Ni
13Co
2Si
4B
2Alloy.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can observe because the thermopositive reaction that the amorphous phase crystallization change causes.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
Embodiment 7 Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1Alloy.
As parent material, element powders purity all is higher than 99.5% with commercial metals element titanium, copper, nickel, aluminium, tin powder and metalloid element silicon, boron powder, and granularity is-200 or-325 orders, and being mixed with nominal composition is Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1Powder mixture.The mechanical mill process of powder mixture is identical with embodiment 1.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1Alloy.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can observe because the thermopositive reaction that heat absorption phenomenon that glass transition causes and amorphous phase crystallization change cause.Ti through mechanical mill in 48 hours formation
50Cu
18Ni
22Al
4Sn
3Si
2B
1The X-ray diffraction spectrum and the hot analytical results of powdered alloy sample are seen Fig. 1 (d) and Fig. 2 (d) respectively.Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1The constitutional features of amorphous powdered alloy and hot analytical results are listed in table 1.
Embodiment 8 Ti
50Cu
13Ni
18Al
12Fe
1Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, copper, nickel, aluminium, iron and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
50Cu
13Ni
18Al
12Fe
1Si
4B
2The nominal composition alloyage after, the preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
50Cu
13Ni
18Al
12Fe
1Si
4B
2Alloy.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can observe because the thermopositive reaction that the amorphous phase crystallization change causes.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
Embodiment 9 Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, copper, nickel, cobalt, palladium and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2The nominal composition alloyage after, the preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2Alloy, the percent by volume of amorphous phase is not less than 50%.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can be observed the thermopositive reaction that is caused by the amorphous phase crystallization change.Ti through mechanical mill in 32 hours formation
50Cu
15Ni
18Co
10Pd
1Si
4B
2The X-ray diffraction spectrum and the hot analytical results of powdered alloy sample are seen Fig. 1 (e) and Fig. 2 (e) respectively.Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2The constitutional features of amorphous powdered alloy and hot analytical results are listed in table 1.
Embodiment 10 Ti
45V
5Cu
19Ni
23Co
2Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, vanadium, copper, nickel, cobalt and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
45V
5Cu
19Ni
23Co
2Si
4B
2The nominal composition alloyage, the preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
45V
5Cu
19Ni
23Co
2Si
4B
2Alloy.The granularity of powder is about 20～100 microns.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
Embodiment 11 Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, niobium, copper, nickel, cobalt and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2The nominal composition alloyage.The preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2Alloy, the percent by volume of amorphous phase is greater than 50%.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can be observed the thermopositive reaction that the crystallization change by amorphous phase causes.Ti through mechanical mill in 48 hours formation
50Nb
5Cu
13Ni
20Co
6Si
4B
2The X-ray diffraction spectrum and the hot analytical results of powdered alloy sample are seen Fig. 1 (f) and Fig. 2 (f) respectively.Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2The constitutional features of amorphous powdered alloy and hot analytical results are listed in table 1.
Embodiment 12 Ti
50Nb
1Fe
1Cu
15Ni
19Al
8Sn
3Si
2B
1Alloy.
With commercial metals element titanium, niobium, iron, copper, nickel, aluminium, tin powder and metalloid element silicon, boron powder is parent material, and element powders purity all is higher than 99.5%, and granularity is-200 or-325 orders, and being mixed with nominal composition is Ti
50Nb
1Fe
1Cu
15Ni
19Al
8Sn
3Si
2B
1Powder mixture.The mechanical mill process of powder mixture is identical with embodiment 1.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
50Nb
1Fe
1Cu
15Ni
19Al
8Sn
3Si
2B
1Alloy.The granularity of powder is about 20～100 microns.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
Embodiment 13 Ti
45Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, zirconium, copper, nickel, iron, cobalt etc. and metalloid element silicon, boron is a parent material, and purity all is higher than 99.5%, according to Ti
45Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2The nominal composition alloyage after.The preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
45Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2Alloy, the percent by volume of amorphous phase is greater than 50%.The granularity of powder is about 20～100 microns.The thermal analysis curve of ball-milled powder can be observed the thermopositive reaction that the crystallization change by amorphous phase causes.The X-ray diffraction spectrum and the hot analytical results of ball milling amorphous powder sample are seen Fig. 1 (g) and Fig. 2 (g) respectively.Ti
45Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2The constitutional features of amorphous powdered alloy and hot analytical results are listed in table 1.
Embodiment 14 Ti
40Mg
10Nb
1Cu
19Ni
23Fe
1Co
1Sn
5Alloy.
Block materials (plate, bar, silk, rod or sheet) with commercial metals element titanium, magnesium, niobium, copper, nickel, iron, cobalt, tin etc. is a parent material, and purity all is higher than 99.5%, according to Ti
40Mg
10Nb
1Cu
19Ni
23Fe
1Co
1Sn
5The nominal composition alloyage after.The preparation of mother alloy chip is identical with embodiment 3 with the mechanical mill process.The powder of ball milling after 48 hours turns out to be amorphous structure through X-ray diffraction, promptly forms amorphous Ti
40Mg
10Nb
1Cu
19Ni
23Fe
1Co
1Sn
5Alloy, the percent by volume of amorphous phase is not less than 50%.The granularity of powder is about 20～100 microns.The constitutional features of ball-milled powder and hot analytical results are listed in table 1.
The constitutional features of 14 kinds of mechanical mill powdered alloys that table 1 embodiment provides and hot analytical results
*
(heating rate is 40K/min)
The T of embodiment powder
gT
xΔ T
x
Alloying constituent (at.%)
Numbering
Phase structure (K) is (K) (K)
1 Ti
45Mg
5Cu
20Ni
24Si
4B
2 Am+Cry 644 761 117
2 Ti
40Mn
10Cu
18Ni
26Si
4B
2 Am -- 773 --
3 Ti
64V
10Fe
1Cu
7Ni
12Si
4B
2 Am+Cry -- 774 --
4 Ti
55Zr
5Fe
2Cu
13Ni
19Si
4B
2 Am+Cry 703 756 53
5 Ti
50Cu
16Ni
20Al
8Si
4B
2 Am 721 781 60
6 Ti
70Cu
9Ni
13Co
2Si
4B
2 Am 698 758 60
7 Ti
50Cu
18Ni
22Al
4Sn
3Si
2B
1 Am 711 775 64
8 Ti
50Cu
13Ni
18Al
12Fe
1Si
4B
2 Am -- 774 --
9 Ti
50Cu
15Ni
18Co
10Pd
1Si
4B
2 Am+Cry -- 753 --
10 Ti
45V
5Cu
19Ni
23Co
2Si
4B
2 Am -- 757 --
11 Ti
50Nb
5Cu
13Ni
20Co
6Si
4B
2 Am+Cry -- 752 --
12 Ti
50Nb
1Fe
1Cu
15Ni
19Al
8Sn
3Si
2B
1 Am -- 763 --
13 Ti
45Zr
5Cu
19Ni
23Fe
1Co
1Si
4B
2 Am+Crv 700 752 52
14 Ti
40Mg
10Nb
1Cu
19Ni
23Fe
1Co
1Sn
5 Am+Cry -- 747 --
*Am represents that alloy forms complete amorphous phase, and Am+Cry represents that alloy is an amorphous phase (Am) and the crystal miscellany of (Cry) mutually; T
gBe glass transformation temperature, T
xBe the starting temperature of amorphous phase crystallization change, Δ T
xWidth (Δ T for the supercooled liquid temperature range
x=T
x-T
g).
Claims (9)
1, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti
aM
b(Cu
xNi
1-x)
cZ
eA wherein, b, c, e are atomic percent, x is an atomic fraction, M is selected from Mg, and Z is selected from least a in B, Ge, Si, C, the Sn element, a=37～77%, b=0.5～27%, c=20～50%, e=1～15%, a+b+c+e=100%, x=0.35～0.75.
2, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti
aM
b(Cu
xNi
1-x)
cZ
eA wherein, b, c, e is an atomic percent, x is an atomic fraction, and M is selected from least a in Mg, Ca, Mn, Nb, Fe, V, Mo, the Zr element, and Z is selected from least a in Sn or Sn and B, the Si element, a=37～77%, b=0.5～27%, c=20～50%, e=1～15%, a+b+c+e=100%, x=0.35～0.75.
3, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti
a(Cu
xNi
1-x)
cR
dZ
e, a wherein, c, d, e are atomic percent, x is an atomic fraction, and R is selected from Al, and Z is selected from least a in B, Ge, Si, C, the Sn element, a=37～77%, c=20～50%, d=0.5～17%, e=1～15%, a+c+d+e=100%, x=0.35～0.75.
4, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti
a(Cu
xNi
1-x)
cR
dZ
e, a wherein, c, d, e are atomic percent, and x is an atomic fraction, R is selected from least a in Al, Ag, Co, Fe, Pd, the Zn element, Z is selected from least a in Sn or Sn and B, the Si element, a=37～77%, c=20～50%, d=0.5～17%, e=1～15%, a+c+d+e=100%, x=0.35～0.75.
5, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti
aM
b(Cu
xNi
1-x)
cR
dZ
e, a wherein, b, c, d, e are atomic percent, x is an atomic fraction, and M is selected from Mg, and R is selected from Al, and Z is selected from least a in B, Ge, Si, C, the Sn element, a=37～77%, b=0.5～27%, c=20～50%, d=0.5～17%, e=1～15%, a+b+c+d+e=100%.x＝0.35～0.75。
6, a kind of multicomponent titanium base alloy that forms amorphous structure is characterized in that the expression formula of alloying constituent is: Ti
aM
b(Cu
xNi
1-x)
cR
dZ
e, a wherein, b, c, d, e are atomic percent, x is an atomic fraction, and M is selected from least a in Mg, Ca, Mn, Nb, Fe, V, Mo, the Zr element, and R is selected from least a in Al, Ag, Co, Pd, the Zn element, Z is selected from least a in Sn or Sn and B, the Si element, a=37～77%, b=0.5～27%, c=20～50%, d=0.5～17%, e=1～15%, a+b+c+d+e=100%.x＝0.35～0.75。
7, according to the described multicomponent titanium base alloy that forms amorphous structure of one of claim 1～6, it is characterized in that: described a=37～70%.
8, according to claim 1,2, the 5 or 6 described multicomponent titanium base alloys that form amorphous structure, it is characterized in that: described b=0.5～20%.
9, according to the described multicomponent titanium base alloy that forms amorphous structure of one of claim 1～6, it is characterized in that: described e=1～12%.
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| CN100372968C (en) * | 2003-04-03 | 2008-03-05 | 南开大学 | NiP amorphous alloy and prep. thereof |
| CN101817087A (en) * | 2010-04-22 | 2010-09-01 | 河北科技大学 | Method for preparing ferrotitanium-based amorphous alloy powder |
| CN106834803A (en) * | 2010-06-14 | 2017-06-13 | 科卢斯博知识产权有限公司 | Stanniferous non-crystaline amorphous metal |
| CN101892444B (en) * | 2010-07-09 | 2012-05-30 | 燕山大学 | Method for preparing Ti50-Fe25-Ni25 ternary amorphous alloy |
| CN102108475B (en) * | 2010-12-11 | 2012-12-26 | 大连理工大学 | Ti-based bulk metallic glass |
| CN102277543B (en) * | 2011-08-09 | 2012-12-05 | 北京科技大学 | Titanium-based block amorphous alloy with high palladium content and low copper content and preparation method thereof |
| CN104801932A (en) * | 2015-04-21 | 2015-07-29 | 常熟锐钛金属制品有限公司 | Production method of high-heat strong titanium pipe |
| CN106319399B (en) * | 2016-09-23 | 2018-07-31 | 北方工业大学 | P-element-containing Ti-based amorphous alloy and preparation method thereof |
| CN110268086A (en) * | 2017-02-07 | 2019-09-20 | Lg电子株式会社 | High-performance solid lubricant titanium amorphous alloy |
| CN108555302B (en) * | 2018-01-22 | 2019-08-30 | 华中科技大学 | A kind of cold increasing material/warm and hot forging combined shaping method of amorphous alloy part |
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