CN102304678B - Gd-Co-Al-Y block metal glass and preparation method thereof - Google Patents
Gd-Co-Al-Y block metal glass and preparation method thereof Download PDFInfo
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- CN102304678B CN102304678B CN201110295609.2A CN201110295609A CN102304678B CN 102304678 B CN102304678 B CN 102304678B CN 201110295609 A CN201110295609 A CN 201110295609A CN 102304678 B CN102304678 B CN 102304678B
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Abstract
The invention relates to Gd-Co-Al-Y block metal glass and a preparation method thereof. The alloy takes Gd as a main element, and the composition of the alloy can be represented by the formula of GdaCobAlcYd, wherein a is larger than or equal to 51.0 and less than or equal to 53.2, b is larger than or equal to 17.0 and less than or equal to 18.5, c is larger than or equal to 25.0 and less than or equal to 29.0, d is larger than or equal to 1.0 and less than or equal to 4.0, and a+b+c+d=100. The preparation method comprises the following steps: proportioning Gd, Co, Al and Y with the purity not less than 99.5% by weight in a specified atom percentage, repeatedly melting the alloy in a titanium-adsorbed argon atmosphere arc furnace until components are uniform so as to obtain a mother alloy cast ingot; and then carrying out water-cooling cooper mould suction casting so as to obtain the block metal glass with the largest diameter of 8 millimeters. The Gd-Co-Al-Y block metal glass provided by the invention has the advantages of high amorphous formation capacity and thermal stability and wide application prospects in the aspects of magnetic cooling functional materials and structural materials.
Description
Technical field
The present invention relates to block metal glass field, particularly relating to a kind of take rare earth as bulk metallic glass materials of matrix and preparation method thereof.
Background technology
Under normal circumstances, solid metal and alloy thereof all exist with crystalline state.Nineteen sixty Duwez finds, under the condition of cooling fast, AuSi system liquid alloy forms non-crystalline state in process of setting, causes the great attention of material supply section educational circles.Preparing in late 1980s the block metal glass that three-dimensional dimension is all greater than 1mm is the developing important milestone of non-crystaline amorphous metal.Different from traditional amorphous thin ribbon utilizing fast quenching to get rid of to be with legal system standby, block metal glass mainly by the Composition Design of alloy, instead of relies on the technique of cooling fast to obtain.At present, under the speed of cooling condition that the foundry engieering of routine can reach, existing more than tens plant alloy system can prepare block metal glass.Result of study in recent years shows, rare earth based block metal glass, such as Gd
60co
26al
14, Ho
30y
26al
24co
20, Er
50al
24co
20y
6deng, having large magnetic entropy becomes and relative refrigerating duty, is suitable as very much magnetic refrigerating working medium and uses.But limited amorphous formation ability and lower thermostability become rare earth based block metal glass huge obstruction on engineer applied.Therefore, the application of rare earth based block metal glass at magnetic refrigerating field to be promoted further, also must continue to put forward heavy alloyed amorphous formation ability and thermostability thereof, prepare larger sized non-crystaline amorphous metal.In addition, the research of block metal glass is that in Materials science and Condensed Matter Physics, some important scientific problems also provide new opportunity.
Existing result of study shows, adopting water cooled copper mould to inhale the method for casting, can be Gd by composition
52.5co
18.5al
29alloy to form greatest circle column diameter be the block metal glass of 3mm, and this alloy also has large magnetic entropy becomes and relative refrigerating duty.Therefore, in this alloy system, mouse out a kind of method prepare the Gd-Co-Al metallic glass with better amorphous formation ability and have very important significance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, adopt the method for alloying, by adopting the method for yttrium Substitute For Partial aluminium on the basis of Gd-Co-Al block metal glass composition, a kind of Gd-Co-Al-Y block metal glass with better amorphous formation ability and thermostability and preparation method thereof is provided, makes it be more suitable for using as magnetic refrigerating working medium.
The present invention is achieved through the following technical solutions, is specially:
Its composition of Gd-Co-Al-Y block metal glass of the present invention and atomic percent are: Gd
aco
bal
cy
d, wherein 51.0≤a≤53.2,17.0≤b≤18.5,25.0≤c≤29.0,1.0≤d≤4.0, and a+b+c+d=100.
Gd-Co-Al-Y block metal glass of the present invention, its component and atomic percent thereof are preferably: Gd
51.7co
18.2al
26.6y
3.5.
Gd-Co-Al-Y block metal glass of the present invention, its component and atomic percent thereof can also be: Gd
53.2co
17.1al
28.7y
1.0.
Gd-Co-Al-Y bulk-metallic glass of the present invention, its maximum diameter is 8 millimeters, and maximum supercooled liquid phase sector width is 77K.
The preparation method of Gd-Co-Al-Y block metal glass of the present invention, it comprises following steps:
(1) by Gd
51.0 ~ 53.2co
17.0 ~ 18.5al
25.0 ~ 29.0y
1.0 ~ 4.0chemical formula weighing; Wherein gadolinium, cobalt, aluminium, the raw-material purity of yttrium are in 99.5%(mass percent) more than;
(2) raw material prepared by step (1) is put into non-consumable arc furnace, be evacuated to 3 × 10
-5more than torr; After high-purity argon gas purging method cleaning 1 ~ 2 time, under 1 atmospheric high-purity argon gas protection, repeatedly overturn melting 4 ~ 6 times, smelting temperature is with till melting sources;
(3) mother alloy melted by step (2) being put into vacuum arc fumace and inhale cast copper crucible, casting cylindric sample by inhaling after alloy melting.
The invention has the advantages that: Gd-Co-Al-Y block metal glass provided by the present invention, the single non-crystal structure that diameter is more than 4mm can be formed, its maximum critical diameter can reach 8mm, the diameter of its non-crystal structure formed much larger than Gd-Co-Al metallic glass.And the Gd-Co-Al-Y block metal glass that inventing provides has higher thermostability, and supercooled liquid phase sector width is maximum can reach 77K, and it is compared Gd-Co-Al metallic glass and has higher thermostability.
The preparation method of Gd-Co-Al-Y block metal glass provided by the invention in addition, has that preparation technology is simple, material microstructure structure is the advantages such as single non-crystal structure.
Accompanying drawing explanation
Fig. 1 is Gd prepared by the embodiment of the present invention 1,2,3,4
53.2co
17.1al
28.7y
1.0, Gd
51.5co
18.0al
28.5y
2.0, Gd
51.7co
18.2al
26.6y
3.5, Gd
52.5co
18.5al
25.0y
4.0the X-ray diffraction spectrum of block metal glass;
Fig. 2 is Gd prepared by the embodiment of the present invention 1,2,3,4
53.2co
17.1al
28.7y
1.0, Gd
51.5co
18.0al
28.5y
2.0, Gd
51.7co
18.2al
26.6y
3.5, Gd
52.5co
18.5al
25.0y
4.0the differential thermal analysis curve of block metal glass.
Embodiment
Embodiment 1:Gd
53.2co
17.1al
28.7y
1.0the preparation of block metal glass and thermostability
Purity is greater than the gadolinium of 99.5% (weight percent), cobalt, aluminium, yttrium raw material by Gd
53.2co
17.1al
28.7y
1.0chemical formula weighing, puts into the argon atmospher non-consumable arc furnace of titanium absorption, utilizes mechanical pump and diffusion pump two-stage vacuum device to be evacuated to 3 × 10 by the raw material prepared
-5more than torr; Utilize high-purity argon gas purging method to clean after 1 ~ 2 time, a standard atmospheric pressure or a little more than the high-purity argon gas protection of 1 standard atmospheric pressure under repeatedly overturn melting and make mother alloy 4 ~ 6 times; The mother alloy melted by above-mentioned steps being put into vacuum arc fumace water-cooled and inhale cast copper crucible, casting inhaling after alloy melting the cylindrical sample that diameter is 4 millimeters.X-ray diffraction analysis shows not find any crystalline diffraction peak in the diffraction spectra of alloy, illustrates that alloy is made up of amorphous phase.Differential scanning calorimetry shows the second-order transition temperature (T of alloy
g) be 598 Kelvins, the initial crystallization temperature (T of alloy
x) be 666 Kelvins, supercooled liquid phase sector width (the Δ T=T of alloy
x-T
g) be 77 Kelvins.
Embodiment 2:Gd
51.5co
18.0al
28.5y
2.0the preparation of block metal glass and thermostability
Purity is greater than the gadolinium of 99.5% (weight percent), cobalt, aluminium, yttrium raw material by Gd
51.5co
18.0al
28.5y
2.0chemical formula weighing, puts into the argon atmospher non-consumable arc furnace of titanium absorption, utilizes mechanical pump and diffusion pump two-stage vacuum device to be evacuated to 3 × 10 by the raw material prepared
-5more than torr; Utilize high-purity argon gas purging method to clean after 1 ~ 2 time, a standard atmospheric pressure or a little more than the high-purity argon gas protection of 1 standard atmospheric pressure under repeatedly overturn melting and make mother alloy 4 ~ 6 times; The mother alloy melted by above-mentioned steps being put into vacuum arc fumace water-cooled and inhale cast copper crucible, casting inhaling after alloy melting the cylindrical sample that diameter is 4 millimeters.X-ray diffraction analysis shows not find any crystalline diffraction peak in the diffraction spectra of alloy, illustrates that alloy is made up of amorphous phase.Differential scanning calorimetry shows the second-order transition temperature (T of alloy
g) be 615 Kelvins, the initial crystallization temperature (T of alloy
x) be 676 Kelvins, supercooled liquid phase sector width (the Δ T=T of alloy
x-T
g) be 61 Kelvins.
Embodiment 3: Gd
51.7co
18.2al
26.6y
3.5the preparation of block metal glass and thermostability
Purity is greater than the gadolinium of 99.5% (weight percent), cobalt, aluminium, yttrium raw material by Gd
51.5co
18al
28.5y
3.5chemical formula weighing, puts into the argon atmospher non-consumable arc furnace of titanium absorption, utilizes mechanical pump and diffusion pump two-stage vacuum device to be evacuated to 3 × 10 by the raw material prepared
-5more than torr; Utilize high-purity argon gas purging method to clean after 1 ~ 2 time, a standard atmospheric pressure or a little more than the high-purity argon gas protection of 1 standard atmospheric pressure under repeatedly overturn melting and make mother alloy 4 ~ 6 times; The mother alloy melted by above-mentioned steps being put into vacuum arc fumace water-cooled and inhale cast copper crucible, casting inhaling after alloy melting the cylindrical sample that diameter is 8 millimeters.X-ray diffraction analysis shows not find any crystalline diffraction peak in the diffraction spectra of alloy, illustrates that alloy is made up of amorphous phase.Differential scanning calorimetry shows the second-order transition temperature (T of alloy
g) be 593 Kelvins, the initial crystallization temperature (T of alloy
x) be 663 Kelvins, supercooled liquid phase sector width (the Δ T=T of alloy
x-T
g) be 70 Kelvins.
Embodiment 4:Gd
52.5co
18.5al
25.0y
4.0the preparation of block metal glass and thermostability
Purity is greater than the gadolinium of 99.5% (weight percent), cobalt, aluminium, yttrium raw material by Gd
52.5co
18.5al
25.0y
4.0chemical formula weighing, puts into the argon atmospher non-consumable arc furnace of titanium absorption, utilizes mechanical pump and diffusion pump two-stage vacuum device to be evacuated to 3 × 10 by the raw material prepared
-5more than torr; Utilize high-purity argon gas purging method to clean after 1 ~ 2 time, a standard atmospheric pressure or a little more than the high-purity argon gas protection of 1 standard atmospheric pressure under repeatedly overturn melting and make mother alloy 4 ~ 6 times; The mother alloy melted by above-mentioned steps being put into vacuum arc fumace water-cooled and inhale cast copper crucible, casting inhaling after alloy melting the cylindrical sample that diameter is 3 millimeters.X-ray diffraction analysis shows not find any crystalline diffraction peak in the diffraction spectra of alloy, illustrates that alloy is made up of amorphous phase.Differential scanning calorimetry shows the second-order transition temperature (T of alloy
g) be 599 Kelvins, the initial crystallization temperature (T of alloy
x) be 653 Kelvins, supercooled liquid phase sector width (the Δ T=T of alloy
x-T
g) be 54 Kelvins.
Embodiment 5 ~ 10:Gd
53.0co
17.0al
29.0y
1.0, Gd
52.5co
18.5al
27.5y
1.5, Gd
52.5co
18.5al
26.5y
2.5, Gd
52.7co
17.0al
28.3y
2.0gd
52.2co
18.5al
26.3y
3.0, Gd
51.0co
18.0al
28.0y
3.0the preparation of block metal glass and thermostability
Purity is greater than the gadolinium of 99.5% (weight percent), cobalt, aluminium, yttrium raw material respectively by Gd
53.0co
17.0al
29.0y
1.0, Gd
52.5co
18.5al
27.5y
1.5, Gd
52.5co
18.5al
26.5y
2.5, Gd
52.7co
17.0al
28.3y
2.0gd
52.2co
18.5al
26.3y
3.0, Gd
51.0co
18.0al
28.0y
3.0chemical formula weighing, puts into the argon atmospher non-consumable arc furnace of titanium absorption, utilizes mechanical pump and diffusion pump two-stage vacuum device to be evacuated to 3 × 10 by the raw material prepared
-5more than torr; Utilize high-purity argon gas purging method to clean after 1 ~ 2 time, a standard atmospheric pressure or a little more than the high-purity argon gas protection of 1 standard atmospheric pressure under repeatedly overturn melting and make mother alloy 4 ~ 6 times; The mother alloy melted by above-mentioned steps being put into vacuum arc fumace water-cooled and inhale cast copper crucible, casting cylindrical sample by inhaling after alloy melting.X-ray diffraction analysis shows not find any crystalline diffraction peak in the diffraction spectra of alloy, illustrates that alloy is made up of amorphous phase.The diameter of its cylindrical sample and shown the second-order transition temperature (T of alloy by differential scanning calorimetry
g), the initial crystallization temperature (T of alloy
x), supercooled liquid phase sector width (the Δ T=T of alloy
x-T
g) as table 1.
The thermal physical property parameter of table 1:Gd-Co-Al-Y block metal glass
Note: 1) in table, symbol implication is as follows:
dcritical size under-this experiment condition;
t g -second-order transition temperature;
t x -crystallization starts temperature;
Δ T=
t x -
t g -supercooled liquid phase sector width.
2) when in table, each components Sample is measured, heating rate used is 20 K/min.
Claims (5)
1. a Gd-Co-Al-Y block metal glass, is characterized in that its composition and atomic percent are: Gd
aco
bal
cy
d, wherein 51.0≤a≤53.2,17.0≤b≤18.5,25.0≤c≤29.0,1.0≤d≤4.0, and a+b+c+d=100.
2. Gd-Co-Al-Y block metal glass according to claim 1, is characterized in that component and atomic percent thereof are: Gd
51.7co
18.2al
26.6y
3.5.
3. Gd-Co-Al-Y block metal glass according to claim 1, is characterized in that component and atomic percent thereof are: Gd
53.2co
17.1al
28.7y
1.0.
4. Gd-Co-Al-Y bulk-metallic glass according to claim 1, it is characterized in that block metal glass maximum diameter is 8 millimeters, maximum supercooled liquid phase sector width is 77K.
5. the preparation method of Gd-Co-Al-Y block metal glass according to claim 1, is characterized in that comprising following steps:
(1) by Gd
51.0 ~ 53.2co
17.0 ~ 18.5al
25.0 ~ 29.0y
1.0 ~ 4.0chemical formula weighing; Wherein gadolinium, cobalt, aluminium, the raw-material purity of yttrium are in 99.5%(mass percent) more than;
(2) raw material prepared by step (1) is put into non-consumable arc furnace, be evacuated to 3 × 10
-5more than torr; After high-purity argon gas purging method cleaning 1 ~ 2 time, under 1 atmospheric high-purity argon gas protection, repeatedly overturn melting 4 ~ 6 times, smelting temperature is with till melting sources;
(3) mother alloy melted by step (2) being put into vacuum arc fumace and inhale cast copper crucible, casting cylindric sample by inhaling after alloy melting.
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CN103409650B (en) * | 2013-07-25 | 2014-11-12 | 北京大学 | Novel method for utilizing hydrogen plasma electric arc melting technology to prepare high-purity rare earth gadolinium elementary substance |
CN106350690B (en) * | 2015-07-17 | 2018-06-26 | 中国科学院物理研究所 | Rare earth gadolinium-based AMORPHOUS ALLOY RIBBONS for room temperature magnetic refrigerating material 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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0193743A1 (en) * | 1985-02-06 | 1986-09-10 | Kabushiki Kaisha Toshiba | Magnetic refrigerant for magnetic refrigeration |
CN101328566A (en) * | 2008-07-30 | 2008-12-24 | 电子科技大学 | Block rare earth gadolinium-based composite amorphous material and preparation thereof |
CN101691645A (en) * | 2009-07-08 | 2010-04-07 | 电子科技大学 | Gd-Co-Al-Zr bulk metallic glass with good amorphous formation ability and preparation method thereof |
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KR100969862B1 (en) * | 2007-12-26 | 2010-07-13 | 연세대학교 산학협력단 | Gd-BASED PHASE SEPARATING METALLIC AMORPHOUS ALLOY HAVING UNIQUE MAGNETIC PROPERTIES |
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EP0193743A1 (en) * | 1985-02-06 | 1986-09-10 | Kabushiki Kaisha Toshiba | Magnetic refrigerant for magnetic refrigeration |
CN101328566A (en) * | 2008-07-30 | 2008-12-24 | 电子科技大学 | Block rare earth gadolinium-based composite amorphous material and preparation thereof |
CN101691645A (en) * | 2009-07-08 | 2010-04-07 | 电子科技大学 | Gd-Co-Al-Zr bulk metallic glass with good amorphous formation ability and preparation method thereof |
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