CN101451223B - Zirconium based amorphous alloy and manufacture method thereof - Google Patents
Zirconium based amorphous alloy and manufacture method thereof Download PDFInfo
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- CN101451223B CN101451223B CN2007101877862A CN200710187786A CN101451223B CN 101451223 B CN101451223 B CN 101451223B CN 2007101877862 A CN2007101877862 A CN 2007101877862A CN 200710187786 A CN200710187786 A CN 200710187786A CN 101451223 B CN101451223 B CN 101451223B
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 33
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 230000000737 periodic effect Effects 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005300 metallic glass Substances 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052713 technetium Inorganic materials 0.000 claims description 4
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims 2
- 239000000956 alloy Substances 0.000 abstract description 16
- 229910045601 alloy Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- 229910052790 beryllium Inorganic materials 0.000 abstract description 10
- 229910052718 tin Inorganic materials 0.000 abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011135 tin Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 230000006698 induction Effects 0.000 description 9
- 239000002178 crystalline material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
- Conductive Materials (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a zirconium-based amorphous alloy. The amorphous alloy contains Zr, Ti, Cu, Ni, Fe and Be, wherein the amorphous alloy also contains Sn and selectively contains ETM and LTM. The ETM can be one or several of elements of IIIB family, IVB family, VB family and VIB family in the periodic table of elements except zirconium and titanium. The LTM can be one or several of elements of IB family, IIB family, VIIB family and VIII family in the periodic table of elements except copper, nickel and iron. The adding of the tin element into the zirconium-based amorphous alloy can effectively improve the amorphous forming capacity of the material. The critical dimension of the amorphous alloy can reach a centimeter level. Simultaneously, due to good plasticity of the alloy, the alloy can avoid sudden failure when bearing load and improve the applicability of the material.
Description
Technical field
The present invention relates to a kind of zirconium-base amorphous alloy and preparation method thereof.
Background technology
Amorphous metal alloy, because of having special structure---the unordered short range order of long-range, and have excellent physics and a chemical property: high strength, high rigidity, wear-resisting, corrosion-resistant, bigger elastic limit and high resistance etc., in addition, also show characteristics such as good supraconductivity and low magnetic loss.Therefore, amorphous metallic material has become the most potential generally acknowledged new structural material, is widely applied to a plurality of fields such as machinery, IT electronics, military project.The appearance of large block amorphous attitude metallic substance has greatly promoted the research and the application of non-crystalline material.
But, some characteristic limitations of non-crystalline material self its application.The problem that presses for solution under the prior art condition has: 1, the production problem of large size non-crystalline material.The unordered structure of long-range to be obtained in process of production, spontaneous the moving of atom in the process of setting will be suppressed at.Rate of cooling is fast more, spontaneous move of atom and the probability of the crystalline material that formation rule is arranged is just more little.But along with the raising of product design size, its inner rate of cooling descends, and inner non-crystallization degree is low, is difficult to form the large size non-crystal structure.The size of the non-crystaline amorphous metal that prior art is produced is generally the 2-10 millimeter.2, effectively improve the problem of the plasticity index of material.Non-crystalline material is because the singularity of self structure, inside can produce various deformation mechanisms and resist deformation unlike crystalline material in carry load, so when stress reaches certain intensity unexpected fracture can take place, cause the generation of disaster accident, seriously restricted the application of amorphous material in the structured material field.Therefore, improve the plasticity of amorphous material also through becoming the focus of this area research at present.
" formation of Zr-Ti-Cu-Ni-Be-Fe block amorphous alloy and amorphous based nano composite material and performance thereof " (Zhao Deqian, Zhang Yong, Pan Mingxiang, Meng Liqin, Wang Weihua. " Acta Metallurgica Sinica " 2000.3) in a kind of Zr-Ti-Cu-Ni-Be-Fe block alloy and preparation method thereof is disclosed, this method forms nanocrystalline composite material by the Fe element that adds molecular fraction 2-10%, and its purpose is to change the susceptibility of material.Along with the increase of iron content, sharp-pointed diffraction peak occurs in the XRD figure, and significantly crystallization phenomenon is promptly arranged, and the iron that the interpolation high level be described influences to some extent to the amorphous formation ability of alloy.This achievement in research can not solve the size and the plasticity problem of non-crystaline amorphous metal.
Summary of the invention
The objective of the invention is provides a kind of centimetre-sized zirconium-base amorphous alloy with good plasticity in order to overcome the little and shortcoming that plasticity is relatively poor of the ubiquitous volume of present amorphous alloy material.
Another object of the present invention provides a kind of preparation method of above-mentioned alloy.
The invention provides a kind of zirconium-base amorphous alloy, this alloy contains Zr, Ti, Cu, Ni, Fe and Be, wherein, this alloy also contains Sn, and optionally contain ETM and LTM, described ETM is one or more in the element except that zirconium and titanium in periodic table of elements IIIB family, IVB family, VB family, the group vib, and described LTM is one or more in the element outside periodic table of elements IB family, IIB family, VIIB family and VIII family copper removal, nickel and the iron.
The present invention also provides the preparation method of above-mentioned alloy; this method is included under the protection of inert gas; the non-crystaline amorphous metal raw material is carried out vacuum melting and cooling forming; wherein; the raw material of described non-crystaline amorphous metal comprises: Zr; Ti; Cu; Ni; Fe; and Be; wherein; the raw material of described non-crystaline amorphous metal also comprises ETM and the LTM that Sn and selectivity contain; described ETM is a periodic table of elements IIIB family; IVB family; VB family; in the element in the group vib except that zirconium and titanium one or both, described LTM are periodic table of elements IB family; IIB family; copper removal in VIIB family and the VIII family; in the element outside nickel and the iron one or both.
Add tin element in the zirconium-base amorphous alloy provided by the invention, can effectively improve the amorphous formation ability of material, the critical size of alloy of the present invention can reach centimetre-sized.Simultaneously, have good plasticity, avoided sudden failure when carry load, improved the applicability of material.
Description of drawings
The accurate ternary phase diagrams of Fig. 1 non-crystaline amorphous metal of the present invention (Zr, Ti, Sn)-(Cu, Ni)-(Be, Fe);
The stress-strain diagram of the non-crystaline amorphous metal that Fig. 2 makes for embodiment 1 and Comparative Examples 1;
The XRD figure of the non-crystaline amorphous metal that Fig. 3 makes for embodiment 1-5 and Comparative Examples 1.
Embodiment
Zirconium-base amorphous alloy provided by the invention has the represented composition of following general formula: (Zr
xTi
ySn
z)
aETM
b(Cu
mNi
n)
cFe
dLTM
eBe
f, wherein, a, b, c, d, e and f are molecular fraction, a+b+c+d+e+f=100, and 30≤a≤75,0≤b≤15,10≤c≤35,0.1≤d≤15,0≤e≤15,0.1≤f≤35; X, y and z are atomic ratio, x+y+z=1, and 0.6≤x≤0.85,0.01x≤z≤0.1x; M and n are atomic ratio, m+n=1, and 0.5≤m≤0.65.
Under the preferable case, 40≤a≤60,0≤b≤10,15≤c≤25,0.5≤d≤5,0≤e≤10,15≤f≤25.
Wherein, ETM is one or more in other elements except that zirconium and titanium in periodic table of elements IIIB family, IVB family, VB family, the group vib, is preferably in scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and the tungsten one or both.LTM is one or more in other element outside copper removal, nickel and the iron in periodic table of elements IB family, IIB family, VIIB family and the VIII family, is preferably in manganese, technetium, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium and the mercury one or both.The summation of element kind is preferably the 1-3 kind among ETM and the LTM.
The accurate ternary phase diagrams of the composition of alloy of the present invention as shown in Figure 1.The determined amorphous of composition variation range of the big parallelogram Regional Representative non-crystaline amorphous metal provided by the invention among the figure forms the zone, and the amorphous that the composition variation range of little parallelogram Regional Representative preferable case is determined forms the zone.The element in the non-crystaline amorphous metal has been represented on leg-of-mutton three summits of outermost respectively, the situation of the alloy described in the figure when not comprising ETM and LTM.The numeral that marks on each among the figure is to represent atoms of elements percentage ratio in the alloy.
The preparation method of zirconium-base amorphous alloy provided by the invention, this method is included under the protection of inert gas, and the non-crystaline amorphous metal raw material is carried out vacuum melting and cooling forming.
The preparation raw material of zirconium-base amorphous alloy provided by the present invention comprises Zr, Ti, Cu, Ni, Fe and Be, and wherein, its preparation raw material also comprises ETM and the LTM that Sn and selectivity contain.
The add-on of various elements will make that the alloy composition of making is the represented composition of following general formula: (Zr
xTi
ySn
z)
aETM
b(Cu
mNi
n)
cFe
dLTM
eBe
f, wherein, a, b, c, d, e and f are molecular fraction, a+b+c+d+e+f=100, and 30≤a≤75,0≤b≤15,10≤c≤35,0.1≤d≤15,0≤e≤15,0.1≤f≤35; X, y and z are atomic ratio, x+y+z=1, and 0.6≤x≤0.85,0.01x≤z≤0.1x; M and n are atomic ratio, m+n=1, and 0.5≤m≤0.65.Under the preferable case, 40≤a≤60,0≤b≤10,15≤c≤25,0.5≤d≤5,0≤e≤10,15≤f≤25.
ETM is one or more in other elements except that zirconium and titanium in periodic table of elements IIIB family, IVB family, VB family, the group vib, is preferably in scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and the tungsten one or both.LTM is one or more in other element outside copper removal, nickel and the iron in periodic table of elements IB family, IIB family, VIIB family and the VIII family, is preferably in manganese, technetium, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium and the mercury one or both.The summation of element kind is preferably the 1-3 kind among ETM and the LTM.
The method of melting of the present invention is the melting method of various routines in this area, as long as with the abundant fusion of non-crystaline amorphous metal raw material, for example, can earlier the non-crystaline amorphous metal raw material be mixed under molten state and is cooled to ingot, then with described ingot remelting.Can be with various alloying element fusions in arc-melting furnace or induction melting furnace, the fused temperature and time is along with the difference of selected heating process has some variations, general melt temperature can be 1000-2700 ℃, be preferably 1500-2000 ℃, fusion time is 5-20 minute, vacuum tightness is not more than 200Pa, is preferably 0.01-5Pa.Reflow process generally adopts arc melting, induction melting or resistance melting, and remelting temperature can be 1000-2300 ℃, is preferably 1000-1500 ℃.Vacuum tightness is not more than 200Pa, is preferably 0.01-5Pa.Described forming method can be the forming method of various routines in this area, for example gets rid of band, copper mold casting, inhales casting, die casting, jet moulding or water quenching, and the speed of cooling of described cooling forming is 10-10
4K/s.Because the critical size difference of different moietys can be selected different mode moulding for use.Described rare gas element is selected from neutral element gas and SF in the periodic table of elements
6In one or more.
Below by embodiment the present invention is described in more detail.
Embodiment 1
Present embodiment is used to illustrate the preparation of zirconium-base amorphous alloy provided by the invention.
With raw material Zr, Ti, Sn, Cu, Ni, Fe, Be altogether 25g according to following ratio: (Zr
0.74Ti
0.25Sn
0.01)
55.34(Cu
0.56Ni
0.44)
20.65Fe
1.96Be
22.05, being positioned in the arc-melting furnace (Shenyang scientific instrument Manufacturing Co., Ltd) and being evacuated to 5Pa, 2000 ℃ of meltings are 6 minutes under the condition of argon shield, are cooled to ingot after fully stirring.With this ingot with 1500 ℃ of fusings of electric-arc heating mode after, with copper mold casting cooling rate 10
2K/s makes zirconium-base amorphous alloy sample C1.
Embodiment 2
Present embodiment is used to illustrate the preparation method of zirconium-base amorphous alloy provided by the invention.
Described according to inventive method, raw material Zr, Ti, Sn, Cu, Ni, Fe, Be are total to 200kg according to (Zr
0.74Ti
0.25Sn
0.01)
55.34(Cu
0.56Ni
0.44)
20.65Fe
1.96Be
22.05Ratio be positioned in the induction melting furnace (middle north science and technology) and be evacuated to 5Pa, 1800 ℃ of meltings are 10 minutes under the condition of argon shield, are cooled to ingot after fully stirring.After the 1200 ℃ of fusings of mode of this ingot, with the method cooling rate 10 of die casting with resistive heating
4K/s makes zirconium-base amorphous alloy sample C2.
Embodiment 3
Present embodiment is used to illustrate the preparation method of zirconium-base amorphous alloy provided by the invention.
With raw material Zr, Ti, Sn, Y, Nb, Cu, Ni, Fe, Be altogether 20g according to following ratio: (Zr
0.80Ti
0.17Sn
0.03)
40Y
5Nb
5(Cu
0.64Ni
0.36)
25Fe
5Be
20, be positioned over and be evacuated to 200Pa in the silica tube, under the condition of argon shield with the mode melting of 2000 ℃ of induction heating 5 minutes), be cooled to ingot after fully stirring.After the 1500 ℃ of fusings of mode of this ingot, with water quenching cooling rate 10 with induction heating
3K/s makes zirconium-base amorphous alloy sample C3.
Embodiment 4
Present embodiment is used to illustrate the preparation method of zirconium-base amorphous alloy provided by the invention.
With raw material Zr, Ti, Sn, Cu, Ni, Co, Fe, Be altogether 200kg according to following ratio: (Zr
0.65Ti
0.29Sn
0.06)
50(Cu
0.5Ni
0.5)
20Co
10Fe
3Be
17, be positioned over and be evacuated to 5Pa in the induction melting furnace, under the condition of argon shield, carried out melting 10 minutes in the mode of 1800 ℃ of induction heating, be cooled to ingot after fully stirring.After the 1000 ℃ of fusings of mode of this ingot, to get rid of band method cooling rate 10 with resistive heating
4K/s makes zirconium-base amorphous alloy sample C4.
Embodiment 5
Present embodiment is used to illustrate the preparation method of zirconium-base amorphous alloy provided by the invention.
With raw material Zr, Ti, Sn, W, Cu, Ni, Pd, Zn, Fe, Be altogether 20g according to following ratio: (Zr
0.75Ti
0.24Sn
0.01)
60W
3(Cu
0.55Ni
0.45)
15Pd
2Zn
1Fe
4Be
15, be positioned over and be evacuated to 2 * 10 in the silica tube
-2Pa with the mode melting of 2000 ℃ of induction heating 5 minutes, is cooled to ingot after fully stirring under the condition of argon shield.After the 1500 ℃ of fusings of mode of this ingot, with water quenching cooling rate 10 with induction heating
4K/s makes zirconium-base amorphous alloy sample C5.
Comparative Examples 1
This Comparative Examples is used to the non-crystalline material that illustrates that prior art makes.
Raw material Zr, Ti, Cu, Ni, Be, Fe are total to 25g according to Zr
41Ti
14Cu
11Ni
9.5Fe
2Be
22.5Ratio is positioned in the arc-melting furnace (Shenyang scientific instrument Manufacturing Co., Ltd) and is evacuated to 5Pa, and 2000 ℃ of meltings are 6 minutes under the condition of argon shield, is cooled to ingot after fully stirring.With this ingot with 1500 ℃ of fusings of electric-arc heating mode after, with copper mold casting cooling rate 10
2K/s makes zirconium-base amorphous alloy sample D1.
Testing method
(1) compression experiment
Be to carry out on 3 tons the CMT5000 serial experiment machine at the tonnage of newly thinking carefully company, loading velocity 0.5 mm/min, the stress-strain situation of specimen C1 and D1, test result is as shown in Figure 2.
(2) hardness test
Hardness is tested on Micro Hardness Text Hv1000 Vickers' hardness test machine, and pressure head weight is 200 grams, and the loading time is 10 seconds, and every kind of sample is got three numerical value, gets its arithmetical av at last, and the result is as shown in table 1.
(3) XRD analysis
Whether the XRD powder diffraction analysis is that material is carried out material phase analysis, be amorphous to judge alloy, and this experiment is to carry out on model is the x-ray powder diffraction instrument of D-MAX2200PC.With the copper target emanation, its incident wavelength λ=1.54060 dusts, acceleration voltage are 40 kilovolts, and electric current is 20 milliamperes, adopt step-scan, and scanning step is 0.04 degree, and test result as shown in Figure 3.
(4) critical size test
The sample of the wedge shape that forms in the copper mold thickness with 1 millimeter from the angle of wedge shape is cut, then aforesaid XRD analysis is carried out in the cross section of cutting back formation, measure structure type, if structure type is a non-crystaline amorphous metal, then continue cutting, till structure type was not non-crystaline amorphous metal, record cutting total thickness, described critical size were this total thickness and deduct thickness after 1 millimeter.The result is as shown in table 1.
Table 1
| Numbering | C1 | C2 | C3 | C4 | C5 | D1 |
| Critical size/mm | ＞14 | ＞14 | 14 | 12 | 12 | 8 |
| Average hardness/Hv | 553 | 553 | 547 | 539 | 548 | 537 |
From the test result of table 1 as can be seen, the critical size of the zirconium-base amorphous alloy that the present invention makes surpasses 1 centimetre, has higher hardness simultaneously.As can be seen from Figure 3, all do not have sharp-pointed diffraction peak to occur in the XRD figure of sample C1, C2, C3, C4, C5 and D1, illustrate that the non-crystallization degree of these alloys is very high.As can be seen from Figure 2, the zirconium-base amorphous alloy D1 that zirconium-base amorphous alloy C1 that the present invention makes and prior art make is when bearing the stress of same intensity, curve overlaps substantially in the stress lower region, but along with stress intensity increases, D1 can only produce very little strain, very fast fracture, and represent the curve of C1 to bend, illustrate that its adaptability to changes obviously is better than D1, i.e. the zirconium-base amorphous alloy that the present invention makes has stronger plasticity.
Claims (10)
1. a zirconium-base amorphous alloy is characterized in that, this non-crystaline amorphous metal has the composition shown in the following general formula: (Zr
xTi
ySn
z)
aETM
b(Cu
mNi
n)
cFe
dLTM
eBe
fWherein, described ETM is one or more in the element except that zirconium and titanium in periodic table of elements IIIB family, IVB family, VB family, the group vib, and described LTM is one or more in the element outside copper removal, nickel and the iron in periodic table of elements IB family, IIB family, VIIB family and the VIII family; A, b, c, d, e and f are molecular fraction, a+b+c+d+e+f=100, and 30≤a≤75,0≤b≤15,10≤c≤35,0.1≤d≤15,0≤e≤15,0.1≤f≤35; X, y and z are atomic ratio, x+y+z=1, and 0.6≤x≤0.85,0.01x≤z≤0.1x; M and n are atomic ratio, m+n=1, and 0.5≤m≤0.65.
2. non-crystaline amorphous metal according to claim 1, wherein, 40≤a≤60,0≤b≤10,15≤c≤25,0.5≤d≤5,0≤e≤10,15≤f≤25.
3. non-crystaline amorphous metal according to claim 1, wherein, described ETM is one or both in scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and the tungsten, described LTM is one or both in manganese, technetium, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium and the mercury, and the summation of element kind is the 1-3 kind among ETM and the LTM.
4. the preparation method of a non-crystaline amorphous metal, this method is included under the protection of inert gas, and the non-crystaline amorphous metal raw material is carried out vacuum melting and cooling forming, and the adding of the raw material of described non-crystaline amorphous metal makes non-crystaline amorphous metal have the composition shown in the following general formula: (Zr
xTi
ySn
z)
aETM
b(Cu
mNi
n)
cFe
dLTM
eBe
fWherein, described ETM is one or more in the element except that zirconium and titanium in periodic table of elements IIIB family, IVB family, VB family, the group vib, and described LTM is one or more in the element outside periodic table of elements IB family, IIB family, VIIB family and VIII family copper removal, nickel and the iron; A, b, c, d, e and f are molecular fraction, a+b+c+d+e+f=100, and 30≤a≤75,0≤b≤15,10≤c≤35,0.1≤d≤15,0≤e≤15,0.1≤f≤35; X, y and z are atomic ratio, x+y+z=1, and 0.6≤x≤0.85,0.01x≤z≤0.1x; M and n are atomic ratio, m+n=1, and 0.5≤m≤0.65.
5. method according to claim 4, wherein, 40≤a≤60,0≤b≤10,15≤c≤25,0.5≤d≤5,0≤e≤10,15≤f≤25.
6. method according to claim 4, wherein, described ETM is one or both in scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and the tungsten, described LTM is one or both in manganese, technetium, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium and the mercury, and the summation of element kind is the 1-3 kind among ETM and the LTM.
7. method according to claim 4, wherein, the method for described vacuum melting comprises mixes the non-crystaline amorphous metal raw material earlier and is cooled to ingot under molten state, then with described ingot remelting.
8. method according to claim 4, wherein, the condition of described vacuum melting comprises that smelting temperature is 1000-2700 ℃, and smelting time is 0.5-5 minute, and vacuum tightness is the 0.01-5 handkerchief.
9. method according to claim 4, wherein, the speed of cooling of described cooling forming is 10-10
4K/s.
10. method according to claim 4, wherein, described rare gas element is selected from neutral element gas and SF in the periodic table of elements
6In one or more.
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| US12/275,560 US20090139612A1 (en) | 2007-11-30 | 2008-11-21 | Zr-based amorphous alloy and a preparing method thereof |
| EP08170293.8A EP2065478B1 (en) | 2007-11-30 | 2008-11-28 | A zr-based amorphous alloy and a preparation method thereof |
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| CN101886232B (en) | 2009-05-14 | 2011-12-14 | 比亚迪股份有限公司 | Amorphous alloy-based composite material and preparation method thereof |
| 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 |
| CN102154596A (en) | 2009-10-30 | 2011-08-17 | 比亚迪股份有限公司 | Zirconium-based amorphous alloy and preparation method thereof |
| WO2011057552A1 (en) | 2009-11-11 | 2011-05-19 | Byd Company Limited | Zirconium-based amorphous alloy, preparing method and recycling method thereof |
| EP2580364A1 (en) | 2010-06-14 | 2013-04-17 | Crucible Intellectual Property, LLC | Tin-containing amorphous alloy |
| CN102383067A (en) * | 2010-08-27 | 2012-03-21 | 比亚迪股份有限公司 | Amorphous alloy powder and preparation method thereof, and amorphous alloy coating and preparation method thereof |
| CN102453845A (en) * | 2010-12-10 | 2012-05-16 | 比亚迪股份有限公司 | Copper-zirconium-based amorphous alloy and preparation method thereof |
| CN102358933B (en) * | 2011-09-28 | 2013-01-16 | 清华大学 | Ti-based block amorphous alloy with great amorphous forming ability and preparation method thereof |
| CN103911563B (en) * | 2012-12-31 | 2017-06-06 | 比亚迪股份有限公司 | Zirconium-base amorphous alloy and preparation method thereof |
| DE102013008396B4 (en) | 2013-05-17 | 2015-04-02 | G. Rau Gmbh & Co. Kg | Method and device for remelting and / or remelting of metallic materials, in particular nitinol |
| US9938605B1 (en) | 2014-10-01 | 2018-04-10 | Materion Corporation | Methods for making zirconium based alloys and bulk metallic glasses |
| US10668529B1 (en) | 2014-12-16 | 2020-06-02 | Materion Corporation | Systems and methods for processing bulk metallic glass articles using near net shape casting and thermoplastic forming |
| CN105779911B (en) * | 2014-12-16 | 2017-10-24 | 辽宁工业大学 | A kind of high-intensity high-tenacity dendrite strengthens titanium-based metal glass composite material |
| CN104858570B (en) * | 2015-03-20 | 2017-01-18 | 江苏科技大学 | High-temperature Zr-based brazing filler metal for brazing of W-Cu alloy and stainless steel, as well as preparation method and welding method |
| EP3447158B1 (en) * | 2017-08-25 | 2020-09-30 | Universität des Saarlandes | Sulfur-containing alloy forming metallic glasses |
| CN110747383B (en) * | 2019-12-10 | 2020-08-04 | 辽宁工业大学 | High-entropy alloy based on intermetallic compound and preparation method thereof |
| CN112210681B (en) * | 2020-09-28 | 2021-10-15 | 中国矿业大学 | Preparation method of zinc-copper-titanium alloy for corrosion prevention |
| CN114032479A (en) * | 2021-11-11 | 2022-02-11 | 盘星新型合金材料(常州)有限公司 | Zr-based bulk amorphous alloy suitable for small electronic equipment and preparation method thereof |
| CN116024507B (en) * | 2022-12-29 | 2024-06-21 | 东莞市逸昊金属材料科技有限公司 | Lightweight amorphous alloy and preparation method thereof |
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