CN100378243C - Holmium base amorphous alloy and its preparation method - Google Patents

Holmium base amorphous alloy and its preparation method Download PDF

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CN100378243C
CN100378243C CNB2005100118146A CN200510011814A CN100378243C CN 100378243 C CN100378243 C CN 100378243C CN B2005100118146 A CNB2005100118146 A CN B2005100118146A CN 200510011814 A CN200510011814 A CN 200510011814A CN 100378243 C CN100378243 C CN 100378243C
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alloy
holmium
amorphous alloy
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arc furnace
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CN1869272A (en
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罗强
赵德乾
潘明祥
汪卫华
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Institute of Physics of CAS
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Abstract

The present invention relates to large holmium-base noncrystalline alloy which uses holmium as the main component. The composition of the alloy can be expressed as Ho<a>MbAl<c>Co<d>Te, wherein 30<=a<=56; 0<=b<=26; 22<=c<=25; 20<=d<=23; 0<=e<=25; a+b+c+d+e=100; the element M is Zr or/and Y; the element T is the transitional metal of Fe, Ni, Nb, Pd, Mo, Hf and Ta or the rare earth elements of Ce, Tb, Dy, Gd, Er and Sm. All the elements of the alloy with purity of not lower than 99.9 wt% are mixed according to the proportion and are repeatedly smelted for multiple times in an arc furnace in a titanium absorbed argon atmosphere, and a mother alloy cast ingot is obtained. Then the mother alloy cast ingot is melted again and the melted body is absorbed into a water-cooled copper mould by using an absorbing casting device in the arc furnace. The alloy has the advantages of need of low critical cooling speed, strong oxygen resisting performance, good crystallization resisting performance, easy formation of noncrystalline alloy of big size, simple preparation, low cost and high thermal stability and can be used in a range of higher temperature.

Description

A kind of holmium base amorphous alloy and preparation method thereof
Technical field
The present invention relates to non-crystaline amorphous metal or metallic glass field, particularly relate to a kind of holmium base large amorphous alloy and preparation method thereof.
Background technology
Non-crystaline amorphous metal or metallic glass normally metal alloy from the liquid cooled to the glass transformation temperature below, before forming core and crystallization, solidify formation.Yet be subjected to the restriction of metal alloy amorphous formation ability, obtain large-sized amorphous bulk, sufficiently high speed of cooling must be arranged.Can obtain high rate of cooling by molten metal or alloy are sprayed onto on the extraordinary conductive substrate of heat conduction, but adopt this method can only obtain strip or powder.
Nearly more than ten years, improvement by alloying constituent optimization design and technology of preparing, people have broken through the restriction of high speed cooling conditions, a series of non-crystaline amorphous metals have been found with stronger inhibition crystallizing power, promptly under low rate of cooling, by the bulk amorphous alloy or the metallic glass of the multiple alloy systems of preparation such as ordinary process method such as die cast, shrend, containment heterogeneous nucleation, directional freeze, powder metallurgy, spray to cast shaping, compaction moulding.Compare with traditional crystal alloy material, bulk amorphous alloys has excellent mechanical property, good processing properties, excellent in chemical activity and magnetic performance, thereby has been applied in many fields such as civilian and military affairs.
In the bulk amorphous alloys that has been found that system, mainly be magnesium-yttrium-transition metal base alloy system, and the preparation of relevant rare earth based alloy system and research are also seldom.And rare earth is as the important strategic resource, because its unique light, electricity and magnetic property are widely used in fields such as medical science, agricultural, metallurgy, chemical industry, oil, environmental protection and novel materials.Therefore, development rare earth based bulk amorphous alloy has broad application prospects.On the one hand, we wish by appropriate design of alloy, make the inhibition crystallization begin required critical cooling rate and reduce, thereby obtain larger sized block rare-earth-base amorphous alloy, satisfy the needs of industrial application; On the other hand, because the glass transition and the crystallization temperature of the light rare earths base large amorphous alloy of having found are lower, its range of application is restricted, and heavy rare earth element has higher fusing point and modulus relatively, we find heavy rare earths bulk amorphous alloys or the metallic glass with higher glass transition and crystallization temperature at expectation, enlarge its range of application.
Summary of the invention
The object of the present invention is to provide a kind ofly have high glass forming ability, suppress crystallizing power strong, can under very low rate of cooling, obtain larger sized holmium base large amorphous alloy, and preparation method thereof.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of holmium base large amorphous alloy, this alloy is main component with the holmium, Ho aM bAl cCo dT e, wherein a, b, c, d and e are that atomic percent and variation range are: 30≤a≤56,0≤b≤26,22≤c≤25,20≤d≤23,0≤e≤25, and a+b+c+d+e=100; Element M is Zr or/and Y, and element T is a transition-metal Fe, Ni, Nb, Pd, Mo, Hf, Ta, or rare earth element ce, Tb, Dy, Gd, Er, Sm.
Described holmium base large amorphous alloy comprises the amorphous phase that is not less than 70% volume percent.
The invention provides a kind of preparation method of above-mentioned holmium base large amorphous alloy, comprise following step:
1) batching: according to above-mentioned chemical formula Ho aM bAl cCo dT eIn each atoms of elements percentage batching;
2) ingot casting: in the electric arc furnace of the argon atmospher that titanium adsorbs, above-mentioned batching is at high temperature melted, and melt back obtains mother alloy ingot to mixing after the cooling;
3) suction casting: use conventional permanent mold casting method, with step 2) the mother alloy ingot refuse that makes utilizes the absorbing and casting device in the electric arc furnace, and the melt suction water-cooled metal mould with mother alloy promptly obtains holmium base large amorphous alloy of the present invention.
The purity of each element raw material all is not less than 99.9wt% (weight percent) in the described step 1).
Holmium base large amorphous alloy provided by the invention and existing non-crystaline amorphous metal are particularly compared with rare-earth-base amorphous alloy, and its advantage is:
1, holmium base large amorphous alloy of the present invention has higher glass forming ability and thermostability, its glass transformation temperature is about 630～690K (357～417 ℃), crystallization temperature is about 690～740K (417～457 ℃), and the width of supercooling liquid phase region is at 44～55K.It is low to form the required critical cooling rate of holmium base large amorphous alloy, and antioxidant capacity is strong, and it is stronger to suppress crystallizing power, is easy to form large-sized non-crystaline amorphous metal, and its size is not less than 1 millimeter in each dimension, and the critical diameter size is not less than 3 millimeters.
2, compare with the rare earth based bulk amorphous alloys of having found, holmium base large amorphous alloy of the present invention has high glass transformation temperature and crystallization temperature, and corresponding high thermostability helps it and is applied in wideer temperature range.
3, China is rare earth big country, and the Mineral resources of holmium are very abundant, and the preparation process of rare earth holmium is simple.The desired holmium of holmium base large amorphous alloy of the present invention is industrial starting material, and its purity is 99.9wt% (weight percent).By contrast, the alloy of its cost and other precious metal-based is low.So development holmium base large amorphous alloy is very suitable for the china natural resources characteristics.
4,, therefore has the potential application prospect because the holmium element has special electronic structure, and its compound has peculiar magnetic property, be widely used in preparing functional materials, and the holmium base amorphous alloy structure is different from crystalline structure.
5, preparation method provided by the invention is simple, and is with low cost.
Description of drawings
Fig. 1 is the X-ray diffractogram of holmium base large amorphous alloy provided by the invention; Wherein be respectively from bottom to up: the Ho of embodiment 3 preparations 39Y 12Al 24Co 20Zr 5, embodiment 6 preparation Ho 40Al 24Co 20Zr 16, embodiment 2 preparation Ho 39Y 16Ali 22Co 23, embodiment 4 preparation Ho 46Y 10Al 24Co 20
Fig. 2 is the Ho of embodiment 1 preparation 40Y 16Al 24Co 20Differential scanning calorimetry (DSC) and differential thermal analysis (DTA) graphic representation (heating rate is 10K/min), illustration is the DTA curve;
Fig. 3 is the Ho of embodiment 2 preparations 39Y 16Al 22Co 23DSC and DTA graphic representation (heating rate is 10K/min);
Fig. 4 is the Ho of embodiment 3 preparations 39Y 12Al 24Co 20Zr 5DSC and DTA graphic representation (heating rate is 10K/min);
Fig. 5 is the Ho of embodiment 4 preparations 46Y 10Al 24Co 20DSC and DTA graphic representation (heating rate is 10K/min).
Fig. 6 is the photo in kind of holmium base large amorphous alloy provided by the invention; Wherein scheme the Ho of a for embodiment 1 preparation 40Y 16Al 24Co 20, figure b is the Ho of embodiment 3 preparations 39Y 12Al 24Co 20Zr 5
Embodiment
Embodiment 1, Ho 40Y 16Al 24Co 20The preparation of holmium base large amorphous alloy.
With material purity is that 99.9% (weight percent) above Ho, Y, Al and four kinds of components of Co are 40: 16: 24 by the molar weight ratio: 20 prepare after, in the electric arc furnace of the argon atmospher that titanium adsorbs, mix and melting, obtain the mother alloy ingot of Ho-Y-Al-Co quad alloy after the cooling; Use conventional metal mould cast method then, with this ingot casting refuse, utilize the absorbing and casting device in the electric arc furnace, the mother alloy melt is sucked water cooled copper mould, can obtain composition is Ho 40Y 16Ali 24Co 20, diameter is the block amorphous alloy of 5mm.Its photo in kind is shown in Fig. 6 a.
Its heat is analyzed (DSC and DTA) as shown in Figure 2, as can be seen from the figure second-order transition temperature (the T of this holmium base large amorphous alloy g), crystallization begins temperature (T x), fusing beginning temperature (T m) and width (the Δ T=T that crosses the cold-zone liquid phase x-T g) be respectively 677.9K, 723.2K, 1050.3K and 45.3K; The second-order transition temperature of this alloy, crystallization begin temperature and fusing beginning temperature all increases, and supercooling liquid phase region broadens and is 45.3K, and this shows that thermostability has improved.Reduction glass temperature (the T of this alloy Rg) and vitrifying index (γ) be respectively 0.645 and 0.407, Ho as can be known 40Y 16Al 24Co 20Still has bigger glass forming ability.
Embodiment 2, Ho 39Y 16Al 22Co 23The preparation of holmium base large amorphous alloy
With the purity of raw material is that 99.9% (weight percent) above Ho, Y, Al and four kinds of components of Co are 39: 16: 22 by the molar weight ratio: 23 prepare after, in the electric arc furnace of the argon atmospher that titanium adsorbs, mix and melting, obtain the mother alloy ingot of Ho-Y-Al-Co quad alloy after the cooling; Use conventional metal mould cast method then, with this ingot casting refuse, utilize the absorbing and casting device in the electric arc furnace, the mother alloy melt is sucked water cooled copper mould, can obtain composition is Ho 39Y 16Al 22Co 23, diameter is the block amorphous alloy of 5mm.
Its X-ray diffraction (XRD) as shown in Figure 1, as can be seen, this alloy is an amorphous alloy completely.
Its heat is analyzed (DSC and DTA) as shown in Figure 3, as can be seen from the figure its second-order transition temperature (T g), crystallization begins temperature (T x), fusing beginning temperature (T m) and width (the Δ T=T that crosses the cold-zone liquid phase x-T g) be respectively 641.4K, 698.6K, 1029.7K and 57.2K; The second-order transition temperature of this alloy, crystallization begin temperature and fusing beginning temperature all increases, and supercooling liquid phase region broadens and is 57.2K, and this shows that thermostability has improved.Reduction glass temperature (the T of this alloy Rg) and vitrifying index (γ) be respectively 0.623 and 0.406, Ho as can be known 39Y 16Ali 22Co 23Still has bigger glass forming ability.
Embodiment 3, Ho 39Y 12Al 24Co 20Zr 5The preparation of holmium base large amorphous alloy
With the purity of raw material is that 99.9% (weight percent) above Ho, Y, Al, Co and five kinds of components of Zr are 39: 12: 24 by the molar weight ratio: after preparing at 20: 5, in the electric arc furnace of the argon atmospher that titanium adsorbs, mix and melting, obtain the mother alloy ingot of Ho-Y-Al-Co-Zr quinary alloy after the cooling; Use conventional metal mould cast method then,, utilize the absorbing and casting device in the electric arc furnace, the mother alloy melt is sucked water cooled copper mould, can obtain the holmium base large amorphous alloy Ho of 3mm this ingot casting refuse 39Y 12Al 24Co 20Zr 5
Its X-ray diffraction (XRD) as shown in Figure 1, as can be seen, this alloy is an amorphous alloy completely.
Its heat is analyzed (DSC and DTA) as shown in Figure 4, as can be seen from the figure: its second-order transition temperature (T g), crystallization begins temperature (T x), fusing beginning temperature (T m) and width (the Δ T=T that crosses the cold-zone liquid phase x-T g) be respectively: 656.7K, 706.9K, 1013K and 50.2K; Reduction glass temperature (the T of this alloy Rg) and vitrifying index (γ) be respectively 0.648 and 0.412.Its photo in kind is shown in Fig. 6 b.
Embodiment 4, Ho 46Y 10Al 24Co 20The preparation of holmium base large amorphous alloy
With the purity of raw material is that 99.9% (weight percent) above Ho, Y, Al, Co and four kinds of components are 46: 10: 24 by the molar weight ratio: 20 prepare after, in the electric arc furnace of the argon atmospher that titanium adsorbs, mix and melting, obtain the mother alloy ingot of Ho-Y-Al-Co quad alloy after the cooling; Use conventional metal mould cast method then, with this ingot casting refuse, utilize the absorbing and casting device in the electric arc furnace, the mother alloy melt is sucked water cooled copper mould, can obtain composition is Ho 46Y 10Al 24Co 20, diameter is the block amorphous alloy of 5mm.
Its X-ray diffraction (XRD) as shown in Figure 1, as can be seen, this alloy is an amorphous alloy completely.
Its heat is analyzed (DSC and DTA) as shown in Figure 5, as can be seen from the figure: its second-order transition temperature (T g), crystallization begins temperature (T x), fusing beginning temperature (T m) and width (the Δ T=T that crosses the cold-zone liquid phase x-T g) be respectively 648.3K, 696.2K, 1025.3K and 47.9K.Reduction glass temperature (the T of this alloy Rg) and vitrifying index (γ) be respectively 0.632 and 0.408.
Embodiment 5～14
Prepare the holmium base large amorphous alloy of various proportionings by the method for embodiment 1, it is formed and thermal physical property parameter is listed in the table 1.
The composition of table 1, holmium base large amorphous alloy and hot rerum natura
Embodiment Alloying constituent D (mm) T g (K) T x (K) T m (K) T l (K) ΔT (K) T rg γ
1 2 3 4 5 6 7 8 9 Ho 40Y 16Al 24Co 20 Ho 39Y 16Al 22Co 23 Ho 39Y 12Al 24Co 20Zr 5 Ho 46Al 24Co 20Y 10 Ho 39Y 16Al 25Co 20 Ho 40Zr 16Al 24Co 20 Ho 44Zr 12Al 24Co 20 Ho 46Y 10Al 22Co 22 Ho 30Y 26Al 24Co 20 5 5 5 5 5 5 5 3 5 677.9 641.4 656.7 648.3 649 683.2 672 653 686 723.2 698.6 706.9 696.2 706 723.3 718 698 730 1050.3 1029.7 1013 1025.3 1030 1050. 1034 1041 1060 1099.8 1057.8 1058.3 1060.1 1071 1100 1092 1070 1112 45.3 57.2 50.2 47.9 58 43.5 46 45 44 0.645 0.623 0.648 0.632 0.630 0.651 0.650 0.627 0.647 0.407 0.406 0.412 0.408 0.411 0.406 0.407 0.405 0.406
10 11 12 13 14 15 16 17 18 19 20 21 Ho 35Y 19Al 23Co 23 Ho 39Zr 17Al 24Co 20 Ho 50Y 6Al 24Co 20 Ho 37Y 13Al 24Co 20Nb 6 Ho 41Y 9Al 24Co 20Hf 6 Ho 34Y 16Al 24Co 20Mo 6 Ho 37Zr 13Al 24Co 20Pd 6 Ho 35Y 15A l24Co 20Fe 6 Ho 30Y 5Al 24Co 20Er 25 Ho 30Y 5Al 24Co 20Dy 25 Ho 42Zr 12Al 24Co 20Y 2 Ho 56Al 24Co 20 5 5 3 3 5 3 5 3 5 3 5 3 642 683 631 675 689 682 686 641 651 635 671 626 696 731 676 722 739 731 738 687 702 683 717 670 1027 1051 1003 1055 1058 1015 1021 1013 1024 1008 1033 1000.1 1053 1094 1042 1076 1100 1053 1050 1055 1062 1051 1088 1043 54 48 45 47 50 49 52 46 51 48 46 44 0.611 0.650 0.611 0.639 0.651 0.648 0.671 0.632 0.635 0.629 0.650 0.625 0.411 0.411 0.404 0.412 0.413 0.421 0.425 0.405 0.409 0.405 0.408 0.401
Annotate: 1) the symbol implication is as follows in the table:
Critical diameter size under D---this experiment condition; T g---second-order transition temperature; T x---crystallization begins temperature; T m---fusing beginning temperature; Δ T=T x-T g---cross the width of cold-zone liquid phase; T Rg---the reduction glass temperature; γ---vitrifying index;
2)T rg＝T g/T m；γ＝T x/(T g+T l)；
3) in the table during each composition sample measurement used heating rate be 10K/min.

Claims (3)

1. holmium base large amorphous alloy, this alloy is main component with the holmium, Ho aM bAl cCo dT e, wherein a, b, c, d and e are that atomic percent and variation range are: 30≤a≤56,0≤b≤26,22≤c≤25,20≤d≤23,0≤e≤25, and a+b+c+d+e=100;
Element M is that Zr is or/and Y;
Element T is transition-metal Fe, Ni, Nb, Pd, Mo, Hf or Ta, or rare earth element ce, Tb, Dy, Gd, Er or Sm.
2. the preparation method of the described holmium base large amorphous alloy of claim 1 comprises following step:
1) batching: according to chemical formula Ho aM bAl cCo dT eEach atoms of elements percentage batching;
Wherein a, b, c, d and e are that atomic percent and variation range are: 30≤a≤56,0≤b≤26,22≤c≤25,20≤d≤23,0≤e≤25, and a+b+c+d+e=100;
Element M is that Zr is or/and Y;
Element T is transition-metal Fe, Ni, Nb, Pd, Mo, Hf or Ta, or rare earth element ce, Tb, Dy, Gd, Er or Sm;
2) ingot casting: in the electric arc furnace of the argon atmospher that titanium adsorbs, above-mentioned batching is at high temperature melted, and melt back obtains mother alloy ingot to mixing after the cooling;
3) suction casting: use conventional permanent mold casting method, with step 2) the mother alloy ingot refuse that makes utilizes the absorbing and casting device in the electric arc furnace, and the melt suction water-cooled metal mould with mother alloy obtains the holmium base large amorphous alloy.
3. the preparation method of holmium base large amorphous alloy as claimed in claim 2 is characterized in that: the purity of each element raw material all is not less than 99.9wt% in the described step 1).
CNB2005100118146A 2005-05-27 2005-05-27 Holmium base amorphous alloy and its preparation method Expired - Fee Related CN100378243C (en)

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CN101191184B (en) * 2006-11-30 2010-11-03 中国科学院物理研究所 Plasticity enhancement massive metal glass material and preparation method thereof
CN101200778B (en) * 2006-12-14 2010-05-19 比亚迪股份有限公司 Method for preparing bulk rare-earth based amorphous alloy
CN101497973B (en) * 2008-01-31 2012-02-22 中国科学院物理研究所 Lutetium based bulk amorphous alloy and preparation thereof
CN101550521B (en) * 2008-04-01 2012-05-23 中国科学院物理研究所 Rare-earth-based bulk amorphous alloy with magnetothermal effect and composite material thereof
CN107419198B (en) * 2017-03-21 2019-03-29 上海大学 Ni-based low temperature amorphous magnetic refrigerating material of Rare-Earth Cobalt and preparation method thereof
CN111321358B (en) * 2020-04-17 2022-02-18 中国科学院物理研究所 Amorphous alloy with spontaneous color change on surface, and preparation method and application thereof

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CN1351191A (en) * 2000-11-01 2002-05-29 中国科学院金属研究所 Nd-Y based amorphous alloy block

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351191A (en) * 2000-11-01 2002-05-29 中国科学院金属研究所 Nd-Y based amorphous alloy block

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