CN1053225C - Method for preparing nanometer materials by solidification reaction - Google Patents
Method for preparing nanometer materials by solidification reaction Download PDFInfo
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- CN1053225C CN1053225C CN96117127A CN96117127A CN1053225C CN 1053225 C CN1053225 C CN 1053225C CN 96117127 A CN96117127 A CN 96117127A CN 96117127 A CN96117127 A CN 96117127A CN 1053225 C CN1053225 C CN 1053225C
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- ultrafine particulate
- alloy
- roasting
- alloy ultrafine
- washing
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Abstract
The present invention relates to a preparation method for superfine microparticles of a transition metal alloy. Solid metal chloride and solid potassium (sodium) borohydride are ground together and then are sintered under nitrogen atmosphere at the temperature of 200 to 450 DEG C, and finally, the superfine microparticles of a boron alloy of noncrystalline metal are obtained after water washing.
Description
The present invention relates to prepare the method for alloy ultrafine particulate, specifically, is a kind of method for preparing the transition metal alloy ultrafine particulate of amorphous nano level with solid state reaction.
Since the Duwez sixties were made amorphous alloy with the rapid quench method, [referring to A.L.Greer, Science 267 (1995) 1947 to have developed the multiple method for preparing amorphous alloy; W.L.Johnson, Progress in Mater.Sci.30 (1986) 81] the high energy mechanical ball milled wherein arranged.This method is the mechanical alloying method under the high energy mechanical ball milling condition with primitive powder mix or different-alloy powder mix.This method is difficult to obtain the non-crystaline amorphous metal component of homogeneous, often has the remnants of some crystalline state components, and the ball milling condition harshness, and what have needs ball milling hundreds of even thousands of hours, [referring to: Liang Guoxian etc. " Materials Science and Engineering " 12 (1994) 47; H.Okumura et al, J.Mater.Sci.27 (1992) 153], so this method product will pollute by the material of ball grinder and ball inevitably, the gained amorphous particles is generally micron order.
Another kind method be liquid phase deposition [referring to J.Van Wonterghem, S.Morup et al., Nature322 (1986) 622; S.Linderoth, Hyperfine Interactions 68 (1991) 107].This method is with KBH in the aqueous solution
4(NaBH
4Deng) the reduction transition metal ion, preparation non-crystalline state transition metal-metalloid alloy ultrafine particulate.The composition of the transition metal alloy that this method makes has certain limitation, with amorphous Fe-B particulate is example, with liquid phase method can only make close B amount less than the alloy of 40at% [referring to Z.HU, Y.Fan, et al., J.Chem, Soc, chem.Commun, 1995,247], and the raw material of this method can not make full use of quite a few KBH
4Or NaBH
4Spontaneous decomposition in the aqueous solution causes very big waste.
The purpose of this invention is to provide a kind of method for preparing the transition metal-metalloid alloy ultrafine particulate of the amorphous of homogeneous, a kind ofly do not need long-time ball milling, but the alloy component modulation, the method for preparing nano level non-crystalline state transition metal-metalloid alloy ultrafine particulate that raw material can make full use of.
Technical solution of the present invention is as follows.
The present invention is the method that adopts solid state reaction, with MXn and M ' YH
4For starting raw material prepares M-Y series alloy ultrafine particulate.
The preparation method of transition metal alloy ultrafine particulate of the present invention is under the anaerobic anhydrous condition, with solid-state MXn and solid-state M ' YH
4Together grind, roasting under nitrogen atmosphere then through water and washing with acetone, promptly get non-crystalline state M-Y alloy ultrafine particulate, or M is a transition metal among the MXn, and X is the fontanel element, and N is the valence mumber of M, formula M ' YH
4Middle M ' is a basic metal, and Y is B or Al.
Transition metal can be Fe, Ni, Co, Pd, Pt etc.
With solid-state MXn and solid-state M ' YH
4After together grinding, 200-450 ℃ of roasting under nitrogen atmosphere, behind water and washing with acetone, purifying promptly got nano level non-crystalline state M-Y alloy ultrafine particulate about 2 days under nitrogen atmosphere.If can get the M-Y alloy ultrafine particulate of crystalline state in high-temperature roasting.
Preparation method of the present invention, MXn and M ' YH
4The mol ratio of consumption can 1.0: 1.0-1.0: 4.4, and the content of gained M-Y alloy Y can be from regulating between the 40at% to 60at%.The granularity of gained ultrafine particulate can be less than 10nm, and the uniformity coefficient of particle is subjected to the time effects of ball milling, and ball milling is more than 8 hours, and the granularity of particle is more even.
With preparation method of the present invention, use anhydrous FeCl
3And M ' BH
4Together grind 200-450 ℃ of roasting under nitrogen atmosphere.Obtain non-crystalline state Fe-B alloy ultrafine particulate through washing.Work as Fecl
3With M ' BH
4Mol ratio is 1: 3.3 o'clock, after grinding, obtains the α-FeB alloy ultrafine particulate of single thing phase in roasting washing more than 700 ℃.
Method of the present invention also can replace anhydrous MX with the MXn that crystal water is arranged, when under oxygen free condition, with MXn and M ' YH that crystal water is arranged
4Grind together, do not need roasting after the grinding, directly washing promptly gets amorphous M-Y alloy ultrafine particulate.Prepare M-Y alloy ultrafine particulate with this, the content in the M-Y alloy generally is lower than 40at%.
The preparation method of transition metal alloy ultrafine particulate of the present invention is a solid state reaction, and is simple to operate, and milling time is short, and what obtain is the transition metal-metalloid alloy ultrafine particulate of non-crystalline state, and granularity can be less than 10nm, and specific surface area can be greater than 50m
2/ g.Since be solid state reaction, raw material M ' YH
4Be fully used, regulate M ' YH
4Consumption, can control the content of Y in the M-Y alloy ultrafine particulate.Therefore be the preparation method of the transition metal that the makes high-quality amorphous-metalloid alloy ultrafine particulate of an economy.
Further specify the present invention by the following examples.Embodiment:
1. (O under height anhydrous and oxygen-free operational condition
2, H
2O reaches the ppm magnitude), take by weighing anhydrous FeCl with 1: 3.3 mol ratio
3And KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, and with the rotating speed ball milling 8h of 160rpm, then roasting 3h under 400 ℃, nitrogen atmosphere protection through washing, passivation, obtains granularity less than 10nm again on planetary ball mill, and specific surface area is greater than 50m
2The Fe of/g
49B
51The non-crystaline amorphous metal particulate.
2. (O under height anhydrous and oxygen-free operational condition
2, H
2O reaches the ppm magnitude), take by weighing anhydrous FeCl with 1: 3.3 mol ratio
3And KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, with the rotating speed ball milling 8h of 160rpm, then roasting 3h under 800 ℃, nitrogen atmosphere protection through washing, passivation, obtains crystalline alpha-FeB ultrafine particulate again on planetary ball mill.
3. (O under height anhydrous and oxygen-free operational condition
2, H
2O reaches the ppm magnitude), take by weighing anhydrous FeCl with 1: 3.3 mol ratio
3And KBH
4, grind 5min to mix slightly, then roasting 3h under 400 ℃, protection of inert gas again through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Fe-B of 52at%.
4. (O under height anhydrous and oxygen-free operational condition
2, H
2O reaches the ppm magnitude), take by weighing anhydrous FeCl with 1: 1.1 mol ratio
3And KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1; on planetary ball mill with the rotating speed ball milling 10h of 160rpm; then roasting 3h under 400 ℃, nitrogen atmosphere protection again through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Fe-B of 40at%.
5. (O under height anhydrous and oxygen-free operational condition
2, H
2O reaches the ppm magnitude), take by weighing anhydrous FeCl with 1: 4.3 mol ratio
3And KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1; on planetary ball mill with the rotating speed ball milling 13h of 160rpm; then roasting 3h under 400 ℃, nitrogen atmosphere protection again through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Fe-B of 60at%.
6. (general N under general anhydrous and oxygen-free operational condition
2Protection), take by weighing anhydrous FeCl with 1: 3.3 mol ratio
3And KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1; on planetary ball mill with the rotating speed ball milling 8h of 160rpm; then roasting 3h under 400 ℃, protection of inert gas again through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Fe-B of 48at%.
7. (general N under general anhydrous and oxygen-free operational condition
2Protection), take by weighing FeCl with 1: 3.3 mol ratio
36H
2O and KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, with the rotating speed ball milling 8h of 160rpm, the B amount that contains that obtains being mixed with a small amount of crystalline phase is the Fe-B superfine alloy particulate of 40at% on planetary ball mill.
8. (general N under general anhydrous and oxygen-free operational condition
2Protection), take by weighing CoCl with 1: 1 mol ratio
26H
2O and KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, with the rotating speed ball milling 6h of 160rpm, through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Co-B of 20at% on planetary ball mill.
9. (general N under general anhydrous and oxygen-free operational condition
2Protection), take by weighing CoCl with 1: 3 mol ratio
26H
2O and KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, with the rotating speed ball milling 6h of 160rpm, through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Co-B of 28at% on planetary ball mill.
10. (general N under general anhydrous and oxygen-free operational condition
2Protection), take by weighing NiCl with 1: 1 mol ratio
26H
2O and KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, with the rotating speed ball milling 6h of 160rpm, through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Ni-B of 16at% on planetary ball mill.
11. (general N under general anhydrous and oxygen-free operational condition
2Protection), take by weighing NiCl with 1: 3 mol ratio
26H
2O and KBH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1, with the rotating speed ball milling 6h of 160rpm, through washing, passivation, obtains containing the B amount and is the nano amorphous alloy particle of Ni-B of 29at% on planetary ball mill.
12. (O under height anhydrous and oxygen-free operational condition
2, H
2O reaches the ppm magnitude), take by weighing anhydrous FeCl with 1: 3.3 mol ratio
3And LiAlH
4, being sealed in the hard stainless steel jar mill, ratio of grinding media to material is 30: 1; on planetary ball mill with the rotating speed ball milling 13h of 160rpm; then roasting 3h under 400 ℃, nitrogen atmosphere protection again through washing, passivation, obtains containing the nano amorphous alloy particle of Fe-Al of the about 50at% of Al amount.
Claims (4)
1. the preparation method of a transition metal alloy ultrafine particulate is characterized in that under the anaerobic anhydrous condition, with solid-state MXn and solid-state M ' YH
4Together grind, then under nitrogen in roasting more than 200 ℃, through washing, promptly get M-Y alloy ultrafine particulate, M is transition-metal Fe, Ni, Co, Pd, Pt among the formula MXn, X is a halogen, n is the valence mumber of M, formula M ' YH
4Middle M is a basic metal, and Y is B, Al.
2. preparation method according to claim 1 is characterized in that 200--450 ℃ of roasting, obtains amorphous M-Y alloy ultrafine particulate, is obtaining the crystal alloy ultrafine particulate more than 600 ℃.
3. preparation method according to claim 1 is characterized in that anhydrous FeCl
3With M ' BH
4Together grind, under nitrogen atmosphere,, obtain amorphous Fe-B alloy ultrafine particulate then, work as FeCl through washing 200--450 ℃ of roasting
3With M ' BH
4Mol ratio is 1: 3.3 o'clock, and after grinding, in roasting more than 700 ℃, washing obtains α-FeB alloy ultrafine particulate.
4. preparation method according to claim 1 is characterized in that regulating MXn and M ' YH
4Consumption, can get the different non-crystalline state M-Y alloy ultrafine particulate of Y containing amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117127A CN1053225C (en) | 1996-10-15 | 1996-10-15 | Method for preparing nanometer materials by solidification reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117127A CN1053225C (en) | 1996-10-15 | 1996-10-15 | Method for preparing nanometer materials by solidification reaction |
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| Publication Number | Publication Date |
|---|---|
| CN1152622A CN1152622A (en) | 1997-06-25 |
| CN1053225C true CN1053225C (en) | 2000-06-07 |
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|---|---|---|---|
| CN96117127A Expired - Fee Related CN1053225C (en) | 1996-10-15 | 1996-10-15 | Method for preparing nanometer materials by solidification reaction |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262129B1 (en) * | 1998-07-31 | 2001-07-17 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| CN1304276C (en) * | 2003-12-04 | 2007-03-14 | 复旦大学 | Aluminum-containing nano complex hydrogen storage material and its preparation method |
| CN103157803B (en) * | 2013-04-17 | 2016-03-30 | 新疆大学 | A kind of solid state reaction prepares the method for Nanoalloy |
| CN109103451A (en) * | 2017-06-21 | 2018-12-28 | 北京大学 | A kind of purposes of lithium-containing transition metal chloride as anode material for lithium-ion batteries |
| CN114472903A (en) * | 2022-02-18 | 2022-05-13 | 江西省科学院应用物理研究所 | Preparation method of superfine iron-boron nano amorphous powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096056A (en) * | 1993-05-29 | 1994-12-07 | 中国科学院金属研究所 | Preparation of iron-base nanometer crystal alloy by complete crystallization method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096056A (en) * | 1993-05-29 | 1994-12-07 | 中国科学院金属研究所 | Preparation of iron-base nanometer crystal alloy by complete crystallization method |
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