CN100595303C - Method of manufacturing single-phase Sm2Co17 nanocrystalline block body material - Google Patents

Abstract

The invention provides a method for preparing a single phase Sm2Co17 nanocrystalline bulk material, belonging to the nano material and novel powder metallurgy technical field. The prior research on the nanocrystal Sm2Co17 alloy concentrates in the alloy systems with two phases or multi-phases. In the method, the metals of Sm and Co are mixed according to the mol ratio of 2 to 17, Sm2Co17 alloy ingots are prepared by the vacuum induction melting; under the protection of argon gas, the alloy ingots are crushed and ground into powder with the particle diameter of less than 500mu m, and the powderis put in a ball milling cylinder for ball milling to prepare non-crystalline alloy powder; the non-crystalline alloy powder is put in a mould for quick sintering forming by utilizing the prior sparkplasma sintering technique so as to prepare the single phase Sm2Co17 nanocrystalline bulk material. The method has the advantages of simple process and strong controllability, and the single phase Sm2Co17 nanocrystalline bulk material prepared by the method has the advantages of complete densification, uniform and fine crystal grains, purified crystal boundary areas and no precipitated phase at the crystal boundary areas, etc.

Description

Single-phase Sm 2Co 17The preparation method of bulk nanometer material

Technical field

The invention belongs to nano material and novel powder metallurgical technology field, be specifically related to a kind of single-phase Sm ₂Co ₁₇The preparation method of bulk nanometer material.

Background technology

Nano material and nanotechnology are the research and development focuses in domestic and international Materials Science and Engineering field from occurring so far always.The unique texture feature that bulk nanometer material has a high-density crystal boundary makes it to compare with traditional coarse-grain block materials and shows significant performance advantage.

Sm ₂Co ₁₇The type alloy because of have superior magnetic property, high thermostability and good solidity to corrosion is widely used in especially occupying critical role especially in fields such as national defence and military projects in the equipment such as precision machine tool, metrical instrument, magnetic bearing and multiple permanent-magnet machine.At present, people are to the Sm of nanometer crystal microstructure ₂Co ₁₇The research of type alloy mainly concentrates on two-phase or multiphase alloy system, and is prepared technology limitation, for single-phase Sm ₂Co ₁₇The research report of bulk nanometer material is few.

Summary of the invention

The object of the present invention is to provide the single-phase Sm of a kind of technical process weak point, good reliability ₂Co ₁₇The preparation method of nanometer crystal alloy block materials.The inventive method can extend to the preparation of multiple single phase nano crystal block body material in the Sm-Co alloy system.

Single-phase Sm provided by the present invention ₂Co ₁₇The preparation method of bulk nanometer material may further comprise the steps:

1) blocky metal Sm and Co are mixed by 23.1%: 76.9% mass ratio, the Co raw material packet is rolled in around the Sm raw material, vacuum induction melting prepares Sm ₂Co ₁₇Alloy cast ingot carries out 2～4 remeltings with alloy cast ingot and handles;

2) with the Sm after the remelting processing ₂Co ₁₇The alloy cast ingot fragmentation, grind to form the powder particle less than 500 μ m, powder particle is packed in the ball grinder by ball material mass ratio 10～20: 1 again, ball milling obtained the complete amorphous powdered alloy in 10～20 hours;

3) amorphous powdered alloy is packed under argon shield sintered-carbide die and coldmoulding; send into and carry out sintering densification in the discharging plasma sintering equipment; sintering process parameter is: the final state sintering temperature is 700～800 ℃; temperature rise rate is 50～100 ℃/min; sintering pressure is 300～500MPa; be not incubated and cool to room temperature after reaching the final state sintering temperature, obtain single-phase Sm ₂Co ₁₇Bulk nanometer material.

Wherein, when raw material mixes in the step 1) Co raw material packet be rolled in the Sm raw material around, can prevent the volatilization loss of Sm in the vacuum melting process; It is in order to obtain the uniform mother metal alloy of composition that alloy cast ingot is carried out the remelting processing; Be further to improve the effect of homogenization of composition, should make top and bottom counter-rotating transposition during the each remelting of ingot casting.

Whether ball material mass ratio step 2) and the decision of ball milling time can obtain amorphous powdered alloy, and directly influence the efficient that ball milling obtains amorphous powder, adopt bigger ratio of grinding media to material to obtain the non-crystalline state powder in the time at short ball milling.

Adopt higher sintering temperature, temperature rise rate and lower sintering pressure sintering temperature, temperature rise rate and the higher sintering pressure equal bulk nanometer material that can obtain densification lower in the step 3) with employing.

The present invention is that the special mechanism of one-tenth phase rule, the decrystallized mechanism of high-energy ball milling and discharge plasma sintering technique according to the Sm-Co alloy proposes.With pure metal Sm, Co is raw material, and the method for utilizing vacuum induction melting to cooperate remelting to handle according to desired alloying constituent can obtain monophasic Sm ₂Co ₁₇Alloy cast ingot.In mechanical milling process, alloy cast ingot does not decompose, but is changed into the powdered alloy of the same race of non-crystal structure by the coarse-grain powder.When amorphous powder is carried out the electrion plasma agglomeration, the good Sm-Co powdered alloy of electroconductibility since pulsed current by the time joule heating effect that produces make powder particle be warmed up to comparatively high temps rapidly, in the process of this high pressure heating, the crystal forming core of nanoscale takes place and grows up in amorphous powder in sintering densification, through the complete crystallization and the densification of amorphous alloy powder, finally prepare fine and close single-phase Sm ₂Co ₁₇The nanometer crystal alloy block materials.

Compared with prior art, the present invention has following beneficial effect:

1) the present invention adopts discharge plasma sintering technique, comes from the rapid intensification of the concurrent joule heating effect of multiple spot, can cause the quickening transmission mechanism of multiple solid phase atom, thereby has significantly quickened the crystallization process of amorphous powder and improved the densification rate of powder; Simultaneously, the sintering pressure that the hundreds of MPa is high quickens the sintering densification process on the one hand, reduce sintering temperature and shorten sintering time, on the other hand, apply the long-range diffusion that high pressure can suppress atom when heating up, thereby control grain coarsening phenomenon nanocrystalline in the process of crystallization and densification effectively.

2) the single-phase Sm for preparing of the inventive method ₂Co ₁₇Bulk nanometer material has been realized complete densification, nanocrystal is evenly tiny in the material microstructure, the pure no precipitated phase in crystal boundary zone, and operational path is simple, flow process short, the controllability of technical parameter is strong, thus guaranteed to obtain the repeatability of ideal material.

Description of drawings

The Sm of preparation among Fig. 1, the embodiment 1 ₂Co ₁₇The X ray diffracting spectrum of alloy cast ingot, amorphous powdered alloy and bulk nanometer.

The single-phase Sm of preparation among Fig. 2, the embodiment 1 ₂Co ₁₇The transmission electron microscope dark field image of bulk nanometer and corresponding selected area electron diffraction collection of illustrative plates, wherein (b) is the high-resolution-ration transmission electric-lens bright field image that regional area amplifies in (a).

The Sm of preparation among Fig. 3, the embodiment 2 ₂Co ₁₇The X ray diffracting spectrum of alloy cast ingot, amorphous powdered alloy and bulk nanometer.

The single-phase Sm of preparation among Fig. 4, the embodiment 2 ₂Co ₁₇The transmission electron microscope dark field image of bulk nanometer and corresponding selected area electron diffraction collection of illustrative plates, wherein (b) is the high-resolution-ration transmission electric-lens bright field image that regional area amplifies in (a).

The invention will be further described below in conjunction with the drawings and specific embodiments.

Embodiment

The purity of raw material Sm and Co is 99.99% among the following embodiment, is provided by Beijing Non-Fervoous Metal Inst..

Embodiment 1

1) little blocky metal Sm and Co are mixed according to 23.1%: 76.9% mass ratio, the Co raw material packet is rolled in around the Sm raw material, adopt and document (Wang Jiang, Zhang Chengyu, Zhang Hui, Yang Zhimao; fourth is held political power: " vacuum induction melting method prepares the CuCr25 alloy ", High-Voltage Electrical Appliances, the 37th phase, the 2nd volume, the 14th page) identical vacuum induction melting step prepares Sm ₂Co ₁₇Alloy cast ingot carries out 2 remeltings with alloy cast ingot and handles;

2) with Sm ₂Co ₁₇The alloy cast ingot fragmentation, grinding to form the powder particle less than 500 μ m, is that 10: 1 ratio is packed in the ball grinder with this powder particle according to ball material mass ratio, and ball milling obtained the complete amorphous powdered alloy in 20 hours;

3) amorphous alloy powder is packed under argon shield sintered-carbide die and coldmoulding; send into and carry out sintering densification in the discharging plasma sintering equipment; adopt following processing parameter: the final state sintering temperature is 700 ℃; temperature rise rate is 50 ℃/min; sintering pressure is 500MPa; be not incubated and cool to room temperature after reaching the final state sintering temperature, obtain density and be 99.8% single-phase Sm ₂Co ₁₇Bulk nanometer material.

Sm ₂Co ₁₇Fig. 1 is seen in the structural analysis of alloy cast ingot, amorphous alloy powder and bulk nanometer, and Fig. 2 is seen in displaing micro tissue topography and high-resolution-ration transmission electric-lens analysis.

Embodiment 2

1) little blocky metal Sm and Co are mixed according to 23.1%: 76.9% mass ratio, the Co raw material packet is rolled in around the Sm raw material, adopt and document (Wang Jiang, Zhang Chengyu, Zhang Hui, Yang Zhimao; fourth is held political power: " vacuum induction melting method prepares the CuCr25 alloy ", High-Voltage Electrical Appliances, the 37th phase, the 2nd volume, the 14th page) identical vacuum induction melting step prepares Sm ₂Co ₁₇Alloy cast ingot carries out 3 remeltings with alloy cast ingot and handles;

2) with Sm ₂Co ₁₇The alloy cast ingot fragmentation, grinding to form the powder particle less than 500 μ m, is that 20: 1 ratio is packed in the ball grinder with this powder particle according to ball material mass ratio, and ball milling obtained the complete amorphous powdered alloy in 10 hours;

3) amorphous alloy powder is packed under argon shield sintered-carbide die and coldmoulding; send into and carry out sintering densification in the discharging plasma sintering equipment; adopt following processing parameter: the final state sintering temperature is 800 ℃; temperature rise rate is 100 ℃/min; sintering pressure is 300MPa; be not incubated and cool to room temperature after reaching the final state sintering temperature, obtain density and be 99.0% single-phase Sm ₂Co ₁₇Bulk nanometer material.

Sm ₂Co ₁₇Fig. 3 is seen in the structural analysis of alloy cast ingot, amorphous alloy powder and bulk nanometer, and Fig. 4 is seen in displaing micro tissue topography and high-resolution-ration transmission electric-lens analysis.

Embodiment 3

1) little blocky metal Sm and Co are mixed according to 23.1%: 76.9% mass ratio, the Co raw material packet is rolled in around the Sm raw material, adopt and document (Wang Jiang, Zhang Chengyu, Zhang Hui, Yang Zhimao; fourth is held political power: " vacuum induction melting method prepares the CuCr25 alloy ", High-Voltage Electrical Appliances, the 37th phase, the 2nd volume, the 14th page) identical vacuum induction melting step prepares Sm ₂Co ₁₇Alloy cast ingot carries out 4 remeltings with alloy cast ingot and handles;

2) with Sm ₂Co ₁₇The alloy cast ingot fragmentation, grinding to form the powder particle less than 500 μ m, is that 12: 1 ratio is packed in the ball grinder with this powder particle according to ball material mass ratio, and ball milling obtained the complete amorphous powdered alloy in 15 hours;

3) amorphous alloy powder is packed under argon shield sintered-carbide die and coldmoulding; send into and carry out sintering densification in the discharging plasma sintering equipment; adopt following processing parameter: the final state sintering temperature is 750 ℃; temperature rise rate is 80 ℃/min; sintering pressure is 400MPa; be not incubated and cool to room temperature after reaching the final state sintering temperature, obtain density and be 99.5% single-phase Sm ₂Co ₁₇Bulk nanometer material.

Claims (1)

1, a kind of single-phase Sm ₂Co ₁₇The preparation method of bulk nanometer material is characterized in that, may further comprise the steps:

1) blocky metal Sm and Co are mixed by 23.1%: 76.9% mass ratio, the Co raw material packet is rolled in around the Sm raw material, vacuum induction melting prepares Sm ₂Co ₁₇Alloy cast ingot carries out 2～4 remeltings with alloy cast ingot and handles;

2) with the Sm after the remelting processing ₂Co ₁₇The alloy cast ingot fragmentation, grind to form the powder particle less than 500 μ m, powder particle is packed in the ball grinder by ball material mass ratio 10～20: 1 again, ball milling obtained the complete amorphous powdered alloy in 10～20 hours;

3) amorphous powdered alloy is packed under argon shield sintered-carbide die and coldmoulding; send into and carry out sintering densification in the discharging plasma sintering equipment; sintering process parameter is: the final state sintering temperature is 700～800 ℃; temperature rise rate is 50～100 ℃/min; sintering pressure is 300～500MPa; be not incubated and cool to room temperature after reaching the final state sintering temperature, obtain single-phase Sm ₂Co ₁₇Bulk nanometer material.

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