CN105671346B - One kind prepares high-purity manganese bismuth(MnBi)The method of alloy - Google Patents

One kind prepares high-purity manganese bismuth(MnBi)The method of alloy Download PDF

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CN105671346B
CN105671346B CN201610092566.0A CN201610092566A CN105671346B CN 105671346 B CN105671346 B CN 105671346B CN 201610092566 A CN201610092566 A CN 201610092566A CN 105671346 B CN105671346 B CN 105671346B
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mnbi
molybdenum cup
powder
alloy
low
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CN105671346A (en
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李海波
贾洪声
鄂元龙
鲁铭
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Jilin Normal University
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Jilin Normal University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/04Making alloys by powder metallurgy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02Compacting only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C22/00Alloys based on manganese

Abstract

The invention belongs to technique is simple, high-purity manganese bismuth(MnBi)The preparation method of alloy.Comprise the following steps:1., choose Bi and Mn powder and be used as raw material;2., by Bi the and Mn powder of above-mentioned 1. middle selection according to a certain ratio, uniform mixing post package carries out low pressure pretreatment to molybdenum cup sample by powder shaping press or carries out super-pressure pretreatment to molybdenum cup sample by domestic cubic hydraulic press in molybdenum cup;3., the molybdenum cup cavity after 2. middle precompressed processing is placed in crucible, the preparation of MnBi alloys is completed by low-temperature sintering, quenching program.Low-temperature sintering is carried out as closed cavity using molybdenum cup, effectively suppresses Bi3+Vaporization at high temperature, prevent Bi, Mn oxide generate, improve the purity of MnBi alloys;Molybdenum cup has high-melting-point, higher oxidizing temperature and high heat conductance, is excellent shielding material and heat conducting material in sintering process and During Quenching.

Description

One kind prepares high-purity manganese bismuth(MnBi)The method of alloy
Technical field
The invention belongs to magnetic functional material research field, specifically a kind of low cost, technique is simple, high-purity, The manganese bismuth of strong operability(MnBi)The preparation method of alloy.
Background technology
MnBi alloy low-temperature phases have NiAs crystal structures, different with strong ferromagnetism and very high magnetocrystalline at normal temperatures Property, its coercivity has positive temperature coefficient(150K-550K), it is the high temperature permanent magnetses material with wide application prospect and practical value Material, meanwhile, MnBi phases have significant magneto-optic effect, can be as magnetooptical memory material, by the wide of domestic and international magnetics researcher General concern.
At present, MnBi alloy preparation methods mainly have magnetic levitation melting method, sputtering method, arc melting method, epitaxial growth method, Induction melting and mechanical alloying etc., Yoshida et al. are prepared for MnBi alloys using arc melting method under He gas atmosphere Content is about 90wt.%MnBi single-phase.J. B. Yang et al. are prepared for MnBi alloy contents using high temperature sintering and magnetic separation technology Bulk sample more than 90wt.%.But in preparation process, due to Bi3+Highly volatile, and Mn is in peritectic reaction at high temperature Easily separated out from liquid phase, cause high-purity MnBi alloy materials to be difficult to synthesize, cause alloy material magnetic property relatively low, and above-mentioned biography The most complex process of method, the cost of system are higher, and these all seriously constrain the application of MnBi alloy materials.Therefore, it can be achieved A kind of low cost, high-purity, the preparation method of the MnBi alloy materials of strong operability is a weight of magnetic functional material research Want developing direction.
The content of the invention
High-purity manganese bismuth is prepared it is an object of the invention to provide one kind(MnBi)The preparation method of alloy, technique letter Single, strong operability is with low cost, can effectively hinder Bi3+Vaporization at high temperature, prevent the generation of Bi, Mn oxide, can be right Bi, Mn content are than being regulated and controled, while hindering MnBi alloys to be decomposed in temperature-fall period by quenching, improve MnBi alloys Purity.
The technical scheme is that:
The preparation method of high-purity MnBi alloys comprises the following steps:
1., choose Bi and Mn powder and be used as raw material;
2., by Bi the and Mn powder of above-mentioned 1. middle selection according to a certain ratio, uniform mixing post package passes through in molybdenum cup Powder shaping press carries out low pressure pretreatment to molybdenum cup sample or carries out superelevation to molybdenum cup sample by domestic cubic hydraulic press Pressure pretreatment;
3., the molybdenum cup cavity after 2. middle precompressed processing is placed in crucible, MnBi is completed by low-temperature sintering, quenching program The preparation of alloy.
Beneficial effects of the present invention are as follows:
1st, the present invention is sealed by precompressed to cavity, excludes the gas in powder, improves powder consistency, Neng Gouyou Effect ground hinders Bi3+Vaporization at high temperature, prevent the generation of Bi, Mn oxide, finally make Bi and Mn mixed-powders generate MnBi it is single-phase.
2nd, the present invention carries out low-temperature sintering using molybdenum cup as closed cavity, effectively suppresses Bi3+Vaporization at high temperature, prevent Only Bi, Mn oxide are generated, and improve the purity of MnBi alloys;Molybdenum cup has high-melting-point, higher oxidizing temperature and hyperpyrexia Conductance, is excellent shielding material and heat conducting material in sintering process and During Quenching.
3rd, high heat conductance large aperture wire netting built in the ceramic crucible that the present invention is used, carrying molybdenum cup cavity, barrier molybdenum cup Cavity is directly contacted with ceramic crucible, reduces its contact area with carrier, and active balance molybdenum cup cavity inner temperature is tied The uniform MnBi alloys of structure, composition.
4th, equipment of the present invention is Muffle furnace, and preparing the method for MnBi alloys has technique simple, strong operability, With low cost, the MnBi alloy structure dense uniforms of synthesis synthesize the advantages of reproducible and purity is high, are that can obtain extensive Production and the method for industrial applications.
Brief description of the drawings
Fig. 1 is molybdenum cup closed cavity body section figure in the present invention.
Fig. 2 is to be used for the sealed pyrophyllite composite block assembling sectional view of the closed cavity precompressed of molybdenum cup in the present invention.
Fig. 3 is sintering cavity sectional view in the present invention.
1-Bi, Mn mixed-powders in figure, 2-molybdenum cup, the closed cavity of 3-molybdenum cup, 4-graphite external member(Graphite-pipe, stone Ink sheet), 5-steel cap, 6-pyrophyllite composite block, 7-ceramic crucible, the closed cavity of 8-molybdenum cup(After precompressed), 9-large aperture Wire netting.
Embodiment
The preparation method of high-purity MnBi alloys comprises the following steps:
1. Bi and Mn powder, is chosen as raw material, nanometer or micron order that described Bi and Mn are 99 %-99.999% Powder.
2., by Bi the and Mn powder of above-mentioned 1. middle selection according to mol ratio 1:x(x=1.0-2.0)Matched, it is uniform mixed Post package is closed in molybdenum cup, low pressure pretreatment is carried out to molybdenum cup sample by powder shaping press or passes through domestic cubic apparatus hydraulic pressure Machine carries out super-pressure pretreatment to molybdenum cup sample, and low pressure Pretreatment pressures scope is 2-40MPa, and pre-press pressure limit is 1-6 GPa。
3., the molybdenum cup cavity after 2. middle precompressed processing is placed in crucible, it is complete by closed low-temperature sintering, quenching program Into the preparation of MnBi alloys, high-purity MnBi alloys are prepared(95 at.%).Closed low-temperature sintering is that ceramic crucible exists Synthesized in Muffle furnace, synthesis temperature is 268-400 DEG C, and the time is 0.5-50h.Crucible includes main body, built in crucible main body The closed cavity of the net loaded molybdenum cup of high heat conductance large aperture metal.
Embodiment 1
As shown in Figure 1:Choose quality 3.0g Bi and Mn mixed-powders(Average grain diameter is 3-5 μm, mol ratio 1:1) As raw material, as shown in Fig. 1 labels 1.Mixed-powder is loaded into outer cup Φ 13.65 × 5 mm, the interior mm of cup Φ 13.38 × 5 Molybdenum cup cavity, as shown in Fig. 1 labels 2.Low pressure precompressed encapsulation process is carried out on powder shaping press, pressure condition is 2 MPa, Obtain the mm molybdenums cups of Φ 14 × 3.2 sealedly densification Bi-Mn sample blocks.
As shown in Figure 3:It is about such as Fig. 3 marks in 40ml ceramic crucible that molybdenum cup sample blocks after sealing are loaded into volume Shown in numbers 7.According to the closed cavity of molybdenum cup(After precompressed)8th, the order of large aperture wire netting 9 from top to bottom is disposed, in horse Not carry out Low Temperature Heat Treatment in stove, sintering temperature is 270 DEG C, soaking time is to obtain the mm of Φ 13.5 × 3 after 50 h, quenching High-purity MnBi alloy cylinder block samples.
Embodiment 2
As shown in Figure 1:Choose quality 3.0g Bi and Mn mixed-powders(Average grain diameter is 3-5 μm, mol ratio 1: 1.3)As raw material, as shown in Fig. 1 labels 1.Mixed-powder is loaded into the mm of outer cup Φ 13.65 × 5, interior cup Φ 13.38 × 5 Mm molybdenum cup cavity, as shown in Fig. 1 labels 2.Low pressure precompressed encapsulation process is carried out on powder shaping press, pressure condition is 15 MPa, obtains the mm molybdenums cups of Φ 14 × 3.2 sealedly densification Bi-Mn sample blocks.
As shown in Figure 3:It is about such as Fig. 3 marks in 40ml ceramic crucible that molybdenum cup sample blocks after sealing are loaded into volume Shown in numbers 7.According to the closed cavity of molybdenum cup(After precompressed)8th, the order of large aperture wire netting 9 from top to bottom is disposed, in horse Not carry out Low Temperature Heat Treatment in stove, sintering temperature is 280 DEG C, soaking time is to obtain the mm of Φ 13.5 × 3 after 20 h, quenching High-purity MnBi alloy cylinder block samples.
Embodiment 3
As shown in Figure 1:Choose quality 3.0g Bi and Mn mixed-powders(Average grain diameter is 3-5 μm, mol ratio 1:2) As raw material, as shown in Fig. 1 labels 1.Mixed-powder is loaded into outer cup Φ 13.65 × 5 mm, the interior mm of cup Φ 13.38 × 5 Molybdenum cup cavity, as shown in Fig. 1 labels 2.Low pressure precompressed encapsulation process is carried out on powder shaping press, pressure condition is 40 MPa, obtains the mm molybdenums cups of Φ 14 × 3.2 sealedly densification Bi-Mn sample blocks.
As shown in Figure 3:It is about such as Fig. 3 marks in 40ml ceramic crucible that molybdenum cup sample blocks after sealing are loaded into volume Shown in numbers 7.According to the closed cavity of molybdenum cup(After precompressed)8th, the order of large aperture wire netting 9 from top to bottom is disposed, in horse Not carry out Low Temperature Heat Treatment in stove, sintering temperature is 400 DEG C, soaking time is that to obtain the mm of Φ 13.5 × 3 after 1 h, quenching high Purity MnBi alloy cylinder block samples.
Embodiment 4
As shown in Figure 1:Choose quality 3.0g Bi and Mn mixed-powders(Average grain diameter is 3-5 μm, mol ratio 1: 1.3)As raw material, as shown in Fig. 1 labels 1.By mixed-powder load for the mm of outer cup Φ 13.65 × 5, interior cup Φ 13.38 × 5 mm molybdenum cup cavity, as shown in Fig. 1 labels 2.
As shown in Figure 2:According to the closed cavity 3 of molybdenum cup, graphite external member(Graphite-pipe, graphite flake)4th, steel cap 5 from it is interior to Outer order is assembled, and is finally put into the lump in pyrophyllite composite block 6, in cubic hinge press(CS-IV types)Enterprising horizontal high voltage Precompressed encapsulation process, pressure condition is that the mm molybdenums cups of Φ 14 × 3.2 sealedly densification Bi-Mn sample blocks are obtained after 1GPa, release.
As shown in Figure 3:It is about such as Fig. 3 marks in 40ml ceramic crucible that molybdenum cup sample blocks after sealing are loaded into volume Shown in numbers 7.According to the closed cavity of molybdenum cup(After precompressed)8th, the order of large aperture wire netting 9 from top to bottom is disposed, in horse Not carry out Low Temperature Heat Treatment in stove, sintering temperature is 270 DEG C, soaking time is to obtain the mm of Φ 13.5 × 3 after 50 h, quenching High-purity MnBi alloy cylinder block samples.
Embodiment 5
As shown in Figure 1:Choose quality 3.0g Bi and Mn mixed-powders(Average grain diameter is 3-5 μm, mol ratio 1: 1.5)As raw material, as shown in Fig. 1 labels 1.Mixed-powder is loaded into the mm of outer cup Φ 13.65 × 5, interior cup Φ 13.38 × 5 Mm molybdenum cup cavity, as shown in Fig. 1 labels 2.
As shown in Figure 2:According to the closed cavity 3 of molybdenum cup, graphite external member(Graphite-pipe, graphite flake)4th, steel cap 5 from it is interior to Outer order is assembled, and is finally put into the lump in pyrophyllite composite block 6, in cubic hinge press(CS-IV types)Enterprising horizontal high voltage Precompressed encapsulation process, pressure condition is that the mm molybdenums cups of Φ 14 × 3.2 sealedly densification Bi-Mn sample blocks are obtained after 3GPa, release.
As shown in Figure 3:It is about such as Fig. 3 marks in 40ml ceramic crucible that molybdenum cup sample blocks after sealing are loaded into volume Shown in numbers 7.According to the closed cavity of molybdenum cup(After precompressed)8th, the order of large aperture wire netting 9 from top to bottom is disposed, in horse Not carry out Low Temperature Heat Treatment in stove, sintering temperature is 290 DEG C, soaking time is to obtain the mm of Φ 13.5 × 3 after 20 h, quenching High-purity MnBi alloy cylinder block samples.
Embodiment 6
As shown in Figure 1:Choose quality 3.0g Bi and Mn mixed-powders(Average grain diameter is 3-5 μm, mol ratio 1: 1.2)As raw material, as shown in Fig. 1 labels 1.Mixed-powder is loaded into the mm of outer cup Φ 13.65 × 5, interior cup Φ 13.38 × 5 Mm molybdenum cup cavity, as shown in Fig. 1 labels 2.
As shown in Figure 2:According to the closed cavity 3 of molybdenum cup, graphite external member(Graphite-pipe, graphite flake)4th, steel cap 5 from it is interior to Outer order is assembled, and is finally put into the lump in pyrophyllite composite block 6, in cubic hinge press(CS-IV types)Enterprising horizontal high voltage Precompressed encapsulation process, pressure condition is that the mm molybdenums cups of Φ 14 × 3.2 sealedly densification Bi-Mn sample blocks are obtained after 6GPa, release.
As shown in Figure 3:It is about such as Fig. 3 marks in 40ml ceramic crucible that molybdenum cup sample blocks after sealing are loaded into volume Shown in numbers 7.According to the closed cavity of molybdenum cup(After precompressed)8th, the order of large aperture wire netting 9 from top to bottom is disposed, in horse Not carry out Low Temperature Heat Treatment in stove, sintering temperature is 400 DEG C, soaking time is that to obtain the mm of Φ 13.5 × 3 after 1 h, quenching high Purity MnBi alloy cylinder block samples.
The invention utilizes low-temperature sintering technology, using the closed sintering cavity of molybdenum cup, synthesizes high-purity MnBi alloy materials, The method produced in enormous quantities with industrial applications can be obtained.

Claims (5)

1. the method that one kind prepares high-purity manganese bismuth (MnBi) alloy, it is characterised in that:This method comprises the following steps:
1., choose Bi and Mn powder and be used as raw material;
2., by Bi the and Mn powder of above-mentioned 1. middle selection according to a certain ratio, uniform mixing post package passes through powder in molybdenum cup Moulding press carries out low pressure pretreatment to molybdenum cup sample or pre- to molybdenum cup sample progress super-pressure by domestic cubic hydraulic press Processing;
3., the molybdenum cup cavity after 2. middle precompressed processing is placed in crucible, MnBi alloys are completed by low-temperature sintering, quenching program Preparation.
The low-temperature sintering is to be synthesized ceramic crucible in Muffle furnace, and synthesis temperature is 268-400 DEG C, and the time is 0.5- 50h, the crucible, including crucible main body, the closed cavity of the net loaded molybdenum cup of high heat conductance large aperture metal built in Crucible body.
2. the method that one kind according to claim 1 prepares high-purity manganese bismuth (MnBi) alloy, it is characterised in that:Described Nanometer or micron powder that Bi and Mn is 99%-99.999%.
3. the method that one kind according to claim 1 prepares high-purity manganese bismuth (MnBi) alloy, it is characterised in that:Described Bi and Mn powder is according to mol ratio 1:1.0-2.0 is matched.
4. the method that one kind according to claim 1 prepares high-purity manganese bismuth (MnBi) alloy, it is characterised in that:The step Suddenly 2. mesolow Pretreatment pressures scope is 2-40Mpa, and pre-press pressure limit is 1-6GPa.
5. the method that one kind according to claim 1 prepares high-purity manganese bismuth (MnBi) alloy, it is characterised in that:It is closed Low-temperature sintering is to be synthesized ceramic crucible in Muffle furnace, and synthesis temperature is 400 DEG C.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
热处理对锰铋合金磁性的影响;钟文定等;《兰州大学学报》;19611231(第2期);第32-38页 *
用粉末冶金法制备锰铋合金的研究;杨正等;《兰州大学学报》;19631231(第1期);第9-14页 *
锰铋合金在不同热处理后的磁性研究;钟文定等;《物理学报》;19620430;第18卷(第4期);第188-193页 *

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