CN1265921C - Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder - Google Patents

Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder Download PDF

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Publication number
CN1265921C
CN1265921C CNB200410081611XA CN200410081611A CN1265921C CN 1265921 C CN1265921 C CN 1265921C CN B200410081611X A CNB200410081611X A CN B200410081611XA CN 200410081611 A CN200410081611 A CN 200410081611A CN 1265921 C CN1265921 C CN 1265921C
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nickel powder
nickel
tap density
yttrium
hydrazine
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CNB200410081611XA
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CN1631589A (en
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何国端
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KAIFEI HIGH ENERGY CHEM INDUCTRY CO Ltd CHENGDU CITY
Chengdu Chemphys Chemical Industry Co Ltd
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KAIFEI HIGH ENERGY CHEM INDUCTRY CO Ltd CHENGDU CITY
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Priority to CNB200410081611XA priority Critical patent/CN1265921C/en
Publication of CN1631589A publication Critical patent/CN1631589A/en
Priority to PCT/CN2005/001861 priority patent/WO2006069513A1/en
Priority to JP2007548671A priority patent/JP4837675B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Abstract

The present invention provides a wet method for manufacturing super-micro sphere metal nickel powder with high tap density. In the method, a bivalent nickel sulphate solution reacts with a mixed solution of sodium hydroxide and sodium carbonate to generate nickel hydroxide and nickel basic salt. Then polyols is added as a shape control agent, rare earth yttrium salt is added as a nucleating agent and hydrazine or hydrazine hydrate is used for reduction. Thus, the method can be used for making out the high-quality metal sphere nickel powder with the advantages of high tap density, narrow grain size distribution, strong oxidation resistance, good dispersibility and controllable average grain size of 0.2 to 1 mu m. The present invention hugely increases the tap density of the nickel powder prepared with the wet method, reduces environment pollution and lowers production cost. The made-out nickel powder can be widely used in industries of MLCC, powder metallurgy, magnetic material, etc.

Description

The wet method manufacture method of high-tap density superfine sphere metallic nickel powder
Technical field:
The invention belongs to the manufacturing technology field of powder body material, special relevant with the wet method manufacture method of high-tap density superfine sphere metallic nickel powder.
Background technology:
The existing method for preparing metal nickel powder is a lot.As: electrolysis, carbonyl thermal decomposition method, vacuum distillation condensation method, mechanical crushing method, pulp High Pressure Hydrogen reducing process and solution reduction method etc.The nickel powder that these methods make is not an out-of-shape, or density is too little, be exactly that manufacturing cost is too high, or particle size distribution is wide.
It generally all is to finish by two steps that liquid phase reduction prepares nickel powder.The first step is prepared the nickel hydroxide colloid at normal temperatures, or the nickelous carbonate colloid, or the basic salt of nickel, belongs to liquid phase and becomes nuclear reaction; Second step was used the hydrazine hydrate reduction nickel hydroxide under the uniform temperature condition, or nickelous carbonate, or the basic salt of nickel, generated metal nickel powder, belonged to oxidation-reduction reaction, and the basic chemical reaction in two steps is:
The flat 4-74810 of Japan adopts hydrazine hydrate and ortho phosphorous acid (or sodium borohydride) to mix reducing agent reduction nickel salt and prepares nickel powder, and its density is little, and granularity is bigger than normal, out-of-shape, and it is serious to reunite.
The flat 5-51610 of Japan adopts the compound of hydrazine or hydrazine directly to reduce Ni (OH) 2, gained nickel powder density is little, and granularity is big, and the powder degree distributes wide, and technology stability is poor.
Shanghai East China University of Science is reducing agent with the hydrazine hydrate, and silver nitrate is a nucleator, and PVP is that protective agent prepares nickel powder.With NiSO 4Solution directly is added drop-wise to and contains Na 2CO 3, in hydrazine hydrate and the PVP mixed liquor, add AgNO again 3Nucleation, the nickel powder granularity that this method makes is bigger than normal, and the PVP consumption is very big, and cost is very high, and has sheet nickel to generate in the reduction process.
The flat 8-246001 of Japan uses NiCl 2The steam gas phase reduction process prepares nickel powder, though be the high-tap density nickel powder, its particle size distribution is wide, the production cost height, and also equipment investment is very big, is not easy to produce on a large scale.
Summary of the invention:
The objective of the invention is to overcome above deficiency, providing a kind of can reduce production costs greatly, density can with NiCl 2The steam gas phase reduction process is comparable, and particle size distribution is very narrow, can be easy to the method for the solution reduction manufactured high-tap density superfine sphere metallic nickel powder of large-scale production.
The object of the present invention is achieved like this:
The wet method manufacture method of high-tap density superfine sphere metallic nickel powder of the present invention, this method is the basic salt that generates nickel hydroxide and nickel with the mixed solution reaction of divalence nickel sulfate solution and NaOH and sodium carbonate, add polyalcohol as the pattern controlling agent, add rare earth yttrium salt and make nucleator, at PH is 8.5～12.5, and temperature is under 40～95 ℃ of conditions, adds the hydrate of hydrazine or hydrazine, the basic salt of reduction nickel hydroxide and nickel makes the superfine sphere metallic nickel powder of high-tap density.
Above-mentioned polyalcohol is at least a kind of in glycerine, butantriol, erythrol, the diethylene glycol (DEG), also can adopt other polyalcohol, rare earth yttrium salt is a kind of in yttrium sulfate, yttrium nitrate, yttrium chloride, acetic acid yttrium, the formic acid yttrium at least, also can adopt other rare earth yttrium salt.
The addition of above-mentioned polyalcohol be in the reaction system nickel weight 10～500%.
The molar concentration of above-mentioned nickel sulfate solution is 0.1～2.5mol/L.
Above-mentioned NaOH (NaOH) and sodium carbonate (Na 2CO 3) NaOH (NaOH) and sodium carbonate (Na in the mixed liquor 2CO 3) weight ratio be (0.2～10): 1.
The consumption of above-mentioned yttrium salt be in the reaction system nickel weight 0.0002～0.2%.
The hydrate concentration of above-mentioned hydrazine or hydrazine is 10～80% (weight percent concentration).
The inventive method is with divalence nickel sulfate solution and NaOH and Na 2CO 3Mixed solution reaction, generate Ni (OH) 2And NiCO 3Ni (OH) 2Precipitation adds polyalcohol and rare earth yttrium salt, is 8.5～12.5 at PH, and temperature is under 40～95 ℃ of conditions, adds the hydrate of hydrazine or hydrazine, reduction Ni (OH) 2And NiCO 3Ni (OH) 2, making average grain diameter is the superfine sphere metallic nickel powder of the controlled high-tap density of 0.2～1.0 μ m.
Characteristics of the present invention are in the reduction system, add polyalcohol, utilize its good peptizaiton and distinctive adsorption property, generate the reunion of nickel powder when stoping reduction effectively.The growth of nickel powder particle all directions is reached unanimity, thereby make the nickel powder good uniformity that produces, smooth surface, good sphericity.Moreover the adding of yttrium salt nucleator has guaranteed that oxidation-reduction reacts smooth and also stably carries out, and has also weakened the magnetic of nickel simultaneously, thereby makes the generation densification more of nickel powder when reducing, thereby obtains the high density nickel powder.
It is 0.2～1 μ m that the present invention can prepare particle mean size, and the high-tap density that particle diameter is controlled, the metal nickel powder of spherical rule, its tap density is big, smooth surface, oxygenation efficiency low (oxygen content＜0.5%), non-oxidizability strong (placing 2 hours oxygen content for 120～140 ℃ in air can not increase), particle size distribution is narrow, as following table:
Average grain diameter (μ m) Particle size distribution (μ m) Tap density (g/cm 3) Specific area (m 2/g)
0.25 0.1-0.4 ≥4.0 ＜2.2
0.45 0.3-0.7 ≥4.5 ＜1.6
0.7 0.4-0.9 ≥4.6 ＜1.5
0.9 0.5-1.2 ≥4.8 ＜1.3
The present invention can greatly reduce environmental pollution, and equipment investment is few, and production cost is low, suitable big suitability for industrialized production, and the nickel powder that produces can be widely used in industries such as MLCC (multi-layer ceramics patch capacitor device), powder metallurgy, magnetic material.
Description of drawings:
Fig. 1 is 0.45 μ m metal nickel powder pattern, granule size and distribution map thereof for the diameter that adopts the inventive method to produce.
Fig. 2 is 0.7 μ m metal nickel powder pattern, granule size and distribution map thereof for the diameter of producing for employing the inventive method.
The specific embodiment:
Embodiment 1:
At volume is in the enamel reaction still of 2000L, adds 1500L deionized water, 19.6 kilograms of NaOH and 3.8 kilograms of Na 2CO 3Stir fully dissolving, add while stirring then about the about 19L of nickel sulfate solution of 1.3mol/L to pH value 12, add 15 kilograms of glycerine again, continue to stir after 30 minutes and begin to be warming up to 70 ℃, the hydrazine hydrate solution and the 0.03 gram nucleator yttrium sulfate that add 44L40% (weight percent concentration) again carry out reduction reaction, and the reaction time is 30 minutes, after reaction finishes after filtration, washing, vacuum drying make metal nickel powder.
The nickel powder that makes by said method is viewed as regular spherical under 20000 times of Electronic Speculum, smooth surface, particle mean size are 0.9 μ m, and particle size distribution is 0.5～1.2 μ m, and tap density is 4.85g/cm 3, specific area is 1.13m 2/ g.
Embodiment 2:
At volume is in the reactor of 2000L, adds 1500L deionized water, 20.8 kilograms of NaOH and 12 kilograms of Na 2CO 3Stir fully dissolving, the about 200L of the nickel sulfate solution left and right sides pH value 11.8 that adds 1.4mol/L then while stirring, add 17 kilograms of butantriols again, continue to stir after 20 minutes and begin to heat up 80 ℃, the hydrazine hydrate 34L and the 0.05 gram nucleator yttrium chloride that add 60% (weight percent concentration) again reduce, and the reaction time is 30 minutes, after reaction finishes after filtration, washing, vacuum drying make metal nickel powder.
The nickel powder that makes by said method is viewed as regular spherical under 20000 times of Electronic Speculum, smooth surface, particle mean size are 0.8 μ m, and particle size distribution is 0.5～1.2 μ m, and tap density is 4.7g/cm 3, specific area is 1.21m 2/ g.
Embodiment 3:
At volume is in the reactor of 2000L, adds 1500L deionized water, 24.5 kilograms of NaOH and 25.2 kilograms of Na 2CO 3, stir fully dissolving after, get 0.05 gram yttrium sulfate and add in the nickel sulfate solution of about 200L1.7mol/L, then while stirring nickel sulfate solution past NaOH, Na 2CO 3Add to pH value 11.7 in the mixed solution, add 10 kilograms of diethylene glycol (DEG)s again, continue to stir after 20 minutes and begin to be warming up to 90 ℃, the hydrazine hydrate 60L that adds 40% (weight percent concentration) again reduces, and reaction in 30 minutes finishes, washing after filtration,, vacuum drying makes the metal nickel powder that average grain diameter is 0.7 μ m (referring to Fig. 2), its good sphericity, smooth surface, narrow particle size distribution, tap density are 4.65g/cm 3
Embodiment 4:
At volume is in the reactor of 2000L, adds 1500L deionized water, 25 kilograms of NaOH and 33.1 kilograms of Na 2CO 3Stir fully dissolving, add while stirring then about the about 200L of nickel sulfate solution of 1.8mol/L to pH value 11.5, add 15 kilograms of erythrol again, continue to stir after 20 minutes and begin to be warming up to 90 ℃, the hydrazine hydrate 32L and the 0.07 gram yttrium sulfate that add 80% (weight percent concentration) again reduce, and reaction in 20 minutes finishes.After filtration, washing, vacuum drying make the smooth, spherical metal nickel powder (referring to Fig. 1) that average grain diameter is 0.45 μ m, tap density is 4.6g/cm 3, particle size distribution range is 0.3 μ m～0.7 μ m, specific area 1.48m 2/ g.
Embodiment 5:
At volume is in the reactor of 2000L, adds 1500L deionized water, 28 kilograms of NaOH and 17.4 kilograms of Na 2CO 3Fully dissolve about the about 200L of nickel sulfate solution that stirs limit adding 2.0mol/L in the back to pH value 11.4, add 30 kilograms of glycerine again, continue to stir after 20 minutes and begin to be warming up to 80 ℃, the hydrazine hydrate 65L and 0.08 yttrium sulfate that add 40% (weight percent concentration) again reduce, and reaction in 20 minutes finishes.After filtration, washing, vacuum drying make the metal nickel powder that average grain diameter is 0.45 μ m, its good sphericity, smooth surface, tap density are 4.5g/cm 3, particle size distribution range is 0.3 μ m～0.9 μ m, specific area 1.45m 2/ g.
Embodiment 6:
At volume is in the reactor of 2000L, adds 1400L deionized water, 42 kilograms of glycerine, 32.4 kilograms of NaOH and 84.4 kilograms of Na 2CO 3Fully dissolve about the about 206L of nickel sulfate solution that stirs limit adding 2.3mol/L in the back to pH value 11, continue stirring and begin to be warming up to 90 ℃ after 20 minutes, the hydrazine hydrate 56L and the 0.1 gram yttrium sulfate that add 60% (weight percent concentration) again reduce, and reaction in 20 minutes finishes.After filtration, washing, vacuum drying make the metal nickel powder that average grain diameter is 0.25 μ m, through 20000 times of electron microscopic observations, its good sphericity, smooth surface, tap density are 4.1g/cm 3, particle size distribution range is 0.1 μ m～0.4 μ m, specific area 1.84m 2/ g.
The various embodiments described above are that foregoing of the present invention is further described, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to the foregoing description.All technology that realizes based on foregoing all belong to scope of the present invention.

Claims (7)

1, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder, it is characterized in that this method is the basic salt that generates nickel hydroxide and nickel with the mixed solution reaction of divalence nickel sulfate solution and NaOH and sodium carbonate, add polyalcohol as the pattern controlling agent, add rare earth yttrium salt and make nucleator, at PH is 8.5～12.5, and temperature is under 40～95 ℃ of conditions, adds the hydrate of hydrazine or hydrazine, the basic salt of reduction nickel hydroxide and nickel makes the superfine sphere metallic nickel powder of high-tap density.
2, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder as claimed in claim 1, it is characterized in that polyalcohol is at least a kind of in glycerine, butantriol, erythrol, the diethylene glycol (DEG), rare earth yttrium salt is a kind of in yttrium sulfate, yttrium nitrate, yttrium chloride, acetic acid yttrium, the formic acid yttrium at least.
3, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder as claimed in claim 1 or 2, the addition that it is characterized in that polyalcohol be in the reaction system nickel weight 10～500%.
4, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder as claimed in claim 1 or 2, the molar concentration that it is characterized in that nickel sulfate solution is 0.1～2.5mol/L.
5, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder as claimed in claim 1 or 2 is characterized in that the weight ratio of NaOH in NaOH and the sodium carbonate mixed liquor and sodium carbonate is (0.2～10): 1.
6, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder as claimed in claim 1 or 2, the consumption that it is characterized in that yttrium salt be in the reaction system nickel weight 0.0002～0.2%.
7, the wet method manufacture method of high-tap density superfine sphere metallic nickel powder as claimed in claim 1 or 2, the hydrate weight percent concentration that it is characterized in that hydrazine or hydrazine is 10～80%.
CNB200410081611XA 2004-12-28 2004-12-28 Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder Active CN1265921C (en)

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CNB200410081611XA CN1265921C (en) 2004-12-28 2004-12-28 Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder
PCT/CN2005/001861 WO2006069513A1 (en) 2004-12-28 2005-11-07 Spherical ultrafine nickel powder with high tap density and its wet processes preparing mothod
JP2007548671A JP4837675B2 (en) 2004-12-28 2005-11-07 High tap density ultrafine spherical metallic nickel powder and wet manufacturing method thereof

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CNB200410081611XA CN1265921C (en) 2004-12-28 2004-12-28 Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder

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CN1265921C true CN1265921C (en) 2006-07-26

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US7601199B2 (en) * 2006-01-19 2009-10-13 Gm Global Technology Operations, Inc. Ni and Ni/NiO core-shell nanoparticles
CN100444433C (en) * 2006-12-27 2008-12-17 河南师范大学 Method of nickel hydroxide surface metallization
CN100436008C (en) * 2007-04-10 2008-11-26 北京科技大学 Chemical production of metal nickel nano-line
CN102423808A (en) * 2011-12-14 2012-04-25 天津工业大学 Quick high concentration synthesizing method of silver nanometer line
CN106270545A (en) * 2015-06-12 2017-01-04 中国振华集团云科电子有限公司 A kind of high-tap density noble metal raw powder's production technology
JP6772646B2 (en) * 2016-08-10 2020-10-21 住友金属鉱山株式会社 Nickel oxide fine powder and its manufacturing method
JP6834235B2 (en) * 2016-08-10 2021-02-24 住友金属鉱山株式会社 Manufacturing method of nickel hydroxide particles
CN112481501B (en) * 2020-11-12 2022-09-27 阳谷祥光铜业有限公司 Method for preparing nickel powder by using decoppering final solution
CN114203326A (en) * 2021-12-13 2022-03-18 中国核动力研究设计院 Graphene-packaged ultrathin nickel-63 radiation source film and preparation method and application thereof
CN114433864A (en) * 2022-01-17 2022-05-06 淮安中顺环保科技有限公司 Preparation method of nano nickel powder

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JPH0474810A (en) * 1990-07-18 1992-03-10 Agency Of Ind Science & Technol Manufacture of nickel base metal fine powder
JP3197454B2 (en) * 1995-03-10 2001-08-13 川崎製鉄株式会社 Ultra fine nickel powder for multilayer ceramic capacitors
JP2991700B2 (en) * 1997-09-11 1999-12-20 三井金属鉱業株式会社 Method for producing nickel fine powder
JP3635451B2 (en) * 1998-09-11 2005-04-06 株式会社村田製作所 Metal powder, method for producing the same, and conductive paste
JP4081987B2 (en) * 2000-05-30 2008-04-30 株式会社村田製作所 Metal powder manufacturing method, metal powder, conductive paste using the same, and multilayer ceramic electronic component using the same
JP4244583B2 (en) * 2002-07-29 2009-03-25 株式会社村田製作所 Conductive paste, method for producing conductive paste, and multilayer ceramic electronic component
JP4059035B2 (en) * 2002-08-20 2008-03-12 株式会社村田製作所 Nickel powder manufacturing method, nickel powder, conductive paste, and multilayer ceramic electronic component

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JP2008525640A (en) 2008-07-17
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JP4837675B2 (en) 2011-12-14

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