CN1060982C - Preparation of ultrafine metal powders - Google Patents
Preparation of ultrafine metal powders Download PDFInfo
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- CN1060982C CN1060982C CN97121904A CN97121904A CN1060982C CN 1060982 C CN1060982 C CN 1060982C CN 97121904 A CN97121904 A CN 97121904A CN 97121904 A CN97121904 A CN 97121904A CN 1060982 C CN1060982 C CN 1060982C
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Abstract
The present invention relates to a preparation method of ultrafine metal powder. In the method, an aqueous solution of metal salts is used as a raw material solution, and the pH value of the raw material solution is regulated to be from 7 to 12 by ammonia water. Alkali is added, and the adding quantity of the alkali is in a molar ratio of 0.07 to 1 of the quantity of the alkali and metal quantity in the raw material solution. Hydrazine hydrate is added, the adding quantity of the hydrazine hydrate in a molar ratio of 0.7 to 5 of the quantity of the hydrazine hydrate and the metal quantity in the raw material solution, and reduction reactions are carried out at 50 to 95 DEG C in stir to generate the ultrafine metal powder. The metal powder can be used for electronic industry, and the method has the advantages of simple equipment, little investment, low product cost, high metal yield and convenient operation.
Description
The present invention relates to a kind of preparation method of super-fine metal powder, the preparation method of the ultra-fine nickel of more specifically saying so, copper, cobalt metal powder.
Along with quick development of modern science and technology, the application of the superfines of various metals and alloy thereof more and more widely, and is also more and more higher to the requirement of its quality.The superfine metal nickel powder can replace noble metal to produce electronic device with nickel in microelectric technique.For example the nickel slurry replaces silver, silver-colored palladium slurry etc.In nickel-cadmium cell production, used extra-fine nickel powder in a large number.In chemical industry, replace palladium or platinum to make catalyst with extra-fine nickel powder.
In order to satisfy the demand of each sciemtifec and technical sphere, the various methods that prepare extra-fine nickel powder constantly occur, and electrolysis is arranged, carbonyl nickel pyrolysismethod, plasma spraying method, pressurized hydrogen reducing process etc.With the each have their own characteristics of the nickel powder of these preparations, just in each technical field, use.
Below respectively produce the method for nickel powder, weak point is all arranged.The nickel powder particle of producing with electrolysis is thicker, and generally its average grain diameter is between 5～15 microns, and size distribution is wide, in more strict powder metallurgy, need sieve sometimes.The plasma spraying method, investment is big, the equipment complexity, operation easier is big.The carbonyl nickel pyrolysismethod, complex process, also there is pollution problem in the production cost height in technology.Wet method pressurized hydrogen reducing process must have strict compressive reaction still.Higher (20～the 40kg/cm of the dividing potential drop of hydrogen in this technical process
2), and metallic has and inhales the hydrogen phenomenon, is restricted in use, needs to carry out dehydrogenation in case of necessity and handles.
Purpose of the present invention just is to work out a kind of new chemical reduction method, produces the inferior spherical super fine nickel powder that every index reaches or be better than the various production methods of above-mentioned prior art.
The preparation method of preparation super-fine metal powder of the present invention (nickel, copper, cobalt) selects suitable reduction system, makes nickel ion, copper ion, cobalt ions be reduced into ultra-fine nickel powder, copper powder, cobalt powder under normal pressure.
The preparation method of a kind of super-fine metal powder of the present invention, said metal powder is a metal nickel powder, copper powder, metal cobalt powder a kind of metal powder wherein, the aqueous solution with copper sulphate, the aqueous solution of copper chloride, the aqueous solution of nickelous sulfate, the aqueous solution of nickel chloride, the aqueous solution of cobaltous sulfate, the aqueous solution of cobalt chloride a kind of aqueous solution wherein is material liquid, as the complexing buffer material liquid is transferred to PH7～12 with ammoniacal liquor, add alkali, the mol ratio that the alkali number that is added is controlled at amount of metal in alkali number/material liquid is 0.07～1, with the hydrazine hydrate is reducing agent, the mol ratio that the amount of the reducing agent hydrazine hydrate that is added is controlled at amount of metal in hydrazine hydrate amount/material liquid is 0.7～5, in stirring, under 50 °～95 ℃ temperature, carry out reduction reaction, and generate ultra-fine metal powder, filter, be washed with water to cleaning solution for neutral, oven dry.
In reaction vessel, for example add material liquid in 3 liters beaker or the enamel reaction still, in wherein a kind of aqueous solution of the aqueous solution of the aqueous solution of the aqueous solution of said material liquid copper sulfate solution, copper chloride, the aqueous solution of nickelous sulfate, nickel chloride, the aqueous solution of cobaltous sulfate, cobalt chloride nickel, copper, cobalt wherein the concentration of a metal ion species be 0.3～4 mol, again with 1.1～1.8 mol for well.The ammoniacal liquor that is added as the complexing buffer can be the ammoniacal liquor of various concentration, is good with concentrated ammonia liquor, and is better with the ammoniacal liquor of 10～14 mol again.With ammoniacal liquor material liquid is adjusted to PH7～12,, adds alkali again for well again with after being adjusted to PH8～11.The alkali that is added can be wherein a kind of of NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate, add alkali form can be the aqueous solution, it can also be solid, the alkali number that is added is that the mol ratio of amount of metal in alkali number/material liquid is 0.07～1, be good with 0.2～0.50 again, under alkali condition, carry out to keep reduction reaction.
The reducing agent that adds is a hydrazine hydrate, can add the aqueous solution that percetage by weight is the hydrazine hydrate of 20-85%.The amount of the reducing agent hydrazine hydrate that is added is that the mol ratio of amount of metal is 0.7～5 in the amount/material liquid of hydrazine hydrate, is good with mol ratio 1.40～2.84 again.Reduction reaction is carried out under 50 °～95 ℃ temperature, and again carrying out under 60～90 ℃ temperature to good, when supernatant does not show the color of metal ion, promptly colourless, reduction reaction has just been finished.Reduction reaction can be finished in 10-120 minute, finished in 10～60 minutes usually, and the speed that stirs in course of reaction does not have remarkable influence to product.
The superfine metal nickel powder that is generated, the superfine metal copper powder, the superfine metal cobalt powder filters with filter paper, filter cloth, is more preferably with the centrifugal filtration of stainless steel filter centrifugal, and it is neutral washing to cleaning solution with ion exchange water or distilled water, oven dry, the temperature of oven dry is controlled at 40～80 ℃, again with 60～80 ℃ for well, temperature is above 80 ℃, oxygen content increases in the super-fine metal powder product, preferably dries in 60-80 ℃ in vacuum drying oven or under inert atmosphere.Said inert atmosphere is argon, nitrogen.
The ultra-fine nickel metal powder that is generated is used electron microscope observation, and its pattern as shown in Figure 1 and Figure 2.Its powder is inferior spherical, and its average grain diameter is less than 0.4 μ m.Measured specific area with the BET method, its specific area is at 1.7～5.6m
2Between/the g, apparent density is less than 0.79g/cm
3
The ultra-fine nickel metal powder of producing with method of the present invention on chemical composition, the product produced of average grain diameter, apparent density, production cost and domestic additive method compares, its comparing result sees Table 1, table 2, table 3.
Table 1 is relevant superfine metal nickel powder chemical spectrum analysis result's comparison both at home and abroad
The domestic electrolysis of element domestic pressurized hydrogen Canada 225 type the present invention produce
Nickel powder reduced nickel powder nickel powder nickel powder
％ ％ ％
Zn 0.0010 ＜0.0037 ＜0.0010 ＜0.0010
Co 0.0016 ＜0.003 0.0020 0.03
Fe 0.017 0.0055 0.0044 0.0086
Cu 0.0011 0.00065 ＜0.0006 ＜0.0006
S 0.004 ＜0.01 0.005 0.01
C 0.14 0.18 0.2 0.019
The cobalt content height mainly is to contain cobalt height (0.44%) in the raw material in the table 1, and sulphur is slightly high, strengthen washing and can further reduce, but carbon content is far below the carbon amount in the nickel powder of other method production.
The nickel powder specific area that table 2 several method is produced, average grain diameter,
The comparison of apparent density, pattern
Powder class specific area average grain diameter apparent density profile
m
2／g μm g／cm
3
Domestic electrolytic nickel powder 0.5 5～15 1.43 dendroids
Domestic carbonyl nickel powder/0.2～3 1.20 zigzags
Domestic pressurized hydrogen is 1.0 0.4～0.6 0.75 round shaped grain shapes also
Former nickel powder
Canada's 225 types 0.7 3.5～5.5 0.20 chains
Nickel powder
The present invention produces 1.7～5.6＜0.4＜0.76 inferior sphere
Nickel powder
Its specific area of the extra-fine nickel powder that method of the present invention is produced is big, and average grain diameter is little, more is applicable to the use of electronic printing slurry.
The contrast of several production method production costs of table 3
Method unit/kilogram nickel powder is annotated
260 82 years data of carbonyl nickel powder
Pressurized hydrogen reduced nickel powder＜100 82 year data
Nickel powder＜100 91 that the inventive method is produced year
The nickel powder that method of the present invention is produced is to produce the minimum method of extra-fine nickel powder cost except that electrolysis.
Advantage of the present invention just is:
1. method technology of the present invention is brief, be easy to grasp, be convenient to enlarge and produce, equipment is simple, and equipment investment is few, energy consumption is low, the cost of product is low, because the surface of newly-generated metallic particles is surrounded by a large amount of gas in reduction reaction, growing up of particle is obstructed, the poly-group of secondary that has stoped simultaneously metallic particles again, therefore the super-fine metal powder function admirable of being produced.Make reducing agent with hydrazine hydrate, do not bring other metal impurities into.
2. method of the present invention is swift in response, and the output capacity height of metal can be up to more than 99%, and the super-fine metal powder of being produced is the superfine metal nickel powder for example, is easy to filter, and is easy to operate.
Electron microscope pattern * 1600 of Fig. 1 product times
Electron microscope pattern * 6000 of Fig. 2 product times
Below the present invention is further illustrated with embodiment, will help method of the present invention and advantage thereof are done further to understand, and the present invention is not subjected to the qualification of these embodiment, and protection scope of the present invention is limited by claims.
Embodiment 1
With nickelous sulfate (NiSO
46H
2O) the aqueous solution is the reduction feed liquid, and the chemical analysis results that contains the nickelous sulfate of 6 crystallizations water shows, contains Ni21.68%, Cu0.0005%, Fe0.001%, Co0.0052%, Zn0.00033%, Pb＜0.002%, water-insoluble 0.011% (more than be percetage by weight).The concentration of nickel metal ion is 1.70 mol in the material liquid, get 1 liter of material liquid in large beaker, with the ammoniacal liquor of 12 mol as the complexing buffer, the PH of material liquid is adjusted to 9.5, add sodium hydroxide solution (its concentration is 25% percetage by weight) again, the amount of the NaOH that is added is that the mol ratio of metallic nickel amount in amount of sodium hydroxide/material liquid is 0.46, carries out under alkali condition to keep reduction reaction.Add the reducing agent hydrazine hydrate, the hydrazine hydrate that is added is the hydrazine hydrate of percetage by weight 85%, and the mol ratio that the amount of the reducing agent hydrazine hydrate that is added is controlled at gold bits nickel amount in hydrazine hydrate amount/material liquid is 1.96, reduction reaction is carried out under 85 ° ± 2 ℃ temperature, reduction reaction was finished at 30 minutes, and centrifugal filtration is neutral with ion-exchange water washing to cleaning solution, dry in vacuum drying chamber at 80 ℃, the chemistry of the superfine metal nickel powder that is generated and spectrum analysis result (percetage by weight) are as follows: As＜0.001, Sb＜0.0003, Bi＜0.0003, Cd＜0.0003, Pb0.00021, Sn＜0.0001, Zn＜0.001, Cu＜0.0006, Mn＜0.0005, Fe0.0036, Co0.001, Al0.001, Si0.0046, Mg0.0098, Ca0.095, S0.016, specific area 5.06m
2/ g, average grain diameter 0.13 μ m, apparent density 0.69g/cm
2, productive rate 99.5%.
Embodiment 2
Its method of operating and the reaction vessel that utilized are with embodiment 1, only different is, the chemical analysis results that contains the nickelous sulfate of 6 crystallizations water is Ni21.38%, Cu0.0005%, Fe0.0005%, Co0.044%, Zn0.0005%, Pb＜0.002%, water-insoluble 0.020% (more than be percetage by weight).Nickel concentration is 2.5 mol in the material liquid, get 1 liter of material liquid, with the ammoniacal liquor of 10 mol as the complexing buffer, it is 8.5 that material liquid is adjusted to PH, the repeated hydrogenation aqueous solution of sodium oxide, the amount of the NaOH that is added is that the mol ratio of metallic nickel amount in amount of sodium hydroxide/material liquid is 0.50, the mol ratio that the amount of the hydrazine hydrate that is added is controlled at metallic nickel amount in hydrazine hydrate amount/material liquid is 2.84, make reduction reaction carry out reduction reaction under 80 ° ± 2 ℃ temperature, reduction reaction was finished at 30 minutes.With ion-exchange water washing to cleaning solution is neutral, dries in vacuum drying chamber at 75 ℃, and the superfine metal nickel powder chemistry and the spectrum analysis result (percetage by weight) that are generated are as follows: As＜0.001, Sb＜0.0003, Bi＜0.0003, Cd＜0.0003, Pb0.00021, Zn＜0.001, Cu＜0.0006, Mn＜0.0005, Fe0.0037, Co0.03, Al0.001, Si0.003, Mg0.01, specific area 1.77m
2/ g, average grain diameter 0.38 μ m, apparent density 0.76g/cm
2, productive rate 99.3%.
Embodiment 3
Its method of operating and the reaction vessel that utilized are with embodiment 1, only different is, the chemical analysis results that contains the nickelous sulfate of 6 crystallizations water is Ni21.88%, Cu0.0005%, Fe0.0005%, Co0.036%, Zn0.0005%, Pb＜0.002%, water-insoluble 0.011% (more than be percetage by weight).Nickel concentration is 0.8 mol in the material liquid, get 1 liter of material liquid, with the ammoniacal liquor of 14 mol as the complexing buffer, material liquid is adjusted to PH11, add sodium hydrate aqueous solution again, the amount of the NaOH that is added is that the mol ratio of metallic nickel amount in amount of sodium hydroxide/material liquid is 0.25, the mol ratio that the amount of the hydrazine hydrate that is added is controlled at metallic nickel amount in hydrazine hydrate amount/material liquid is 1.40, the concentration of the aqueous solution of the hydrazine hydrate that is added is 35% (percetage by weight), make reduction reaction under 70 ° ± 2 ℃ temperature, carry out reduction reaction, reduction reaction was finished at 30 minutes, was neutral with ion-exchange water washing to cleaning solution.Dry in vacuum drying chamber at 70 ℃, the chemistry of the ultra-fine genus nickel powder that is generated and spectrum analysis result (percetage by weight) are as follows: As＜0.001, Sb＜0.0003, Bi＜0.0003, Cd＜0.0003, Sn＜0.0001, Zn＜0.001, Cu0.0006, Mn＜0.0005, Fe0.004Co0.022, Al0.001, Si0.0062, Mg0.010, specific area 4.15m
2/ g, average grain diameter 0.16 μ m, apparent density 0.45g/cm
2, productive rate～100%.
Embodiment 4
Its method of operating and the reaction vessel that is utilized and conditionally complete are with embodiment 4, and only different is the aqueous solution of material liquid with copper sulphate, and the specific area of the superfine cupper powder of generation is 5.00m
2/ g, average grain diameter 0.14 μ m, apparent density 0.71g/cm
2, productive rate 99.6%.
Embodiment 5
Its method of operating and the reaction vessel that is utilized and conditionally complete are with embodiment 1, and only different is the material liquid cobalt sulfate solution, and the specific area of the super-fine cobalt powder of generation is 5.01m
2/ g, average grain diameter 0.13 μ m, apparent density 0.68g/cm
2, productive rate 99.7%.
Claims (10)
1. the preparation method of a super-fine metal powder, said super-fine metal powder is metal nickel powder, copper powder, metal cobalt powder a kind of metal powder wherein, with the aqueous solution of copper sulphate, the aqueous solution of copper chloride, the aqueous solution of nickelous sulfate, the aqueous solution of nickel chloride, the aqueous solution of cobaltous sulfate, the aqueous solution a kind of aqueous solution wherein of cobalt chloride is material liquid, it is characterized in that
1) as the complexing buffer material liquid is transferred to PH7～12 with ammoniacal liquor,
2) add alkali, the mol ratio that the alkali number that is added is controlled at amount of metal in alkali number/material liquid is 0.07～1,
3) with the hydrazine hydrate be reducing agent, add the reducing agent hydrazine hydrate the amount mol ratio that is controlled at amount of metal in hydrazine hydrate amount/material liquid be 0.7～5, in stirring, under 50 °～95 ℃ temperature, carry out reduction reaction, generate super-fine metal powder.
4) filter, be washed with water to cleaning solution for neutral, oven dry.
2. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that the concentration of nickel, copper, a cobalt metal ion species wherein is the 0.3-4 mol in the material liquid.
3. according to the preparation method of a kind of super-fine metal powder of claim 2, it is characterized in that, in the material liquid nickel, copper, cobalt wherein the concentration of a metal ion species be the 1.1-1.8 mol.
4. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that, material liquid is transferred to PH8～11 with ammoniacal liquor.
5. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that said alkali is wherein a kind of of NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate.
6. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that the alkali number of adding is that the mol ratio of amount of metal in alkali number/material liquid is 0.2～0.50.
7. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that the amount of the reducing agent hydrazine hydrate that is added is that the mol ratio of amount of metal in hydrazine hydrate amount/material liquid is 1.40～2.84.
8. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that reduction reaction is carried out under 60-90 ℃ temperature.
9. according to the preparation method of a kind of super-fine metal powder of claim 1, it is characterized in that bake out temperature is 40-80 ℃.
10. according to the preparation method of a kind of super-fine metal powder of claim 9, it is characterized in that, in vacuum drying oven or under inert atmosphere, dry in 60～80 ℃.
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Cited By (1)
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| CN1300381C (en) * | 2003-06-16 | 2007-02-14 | 昆明理工恒达科技有限公司 | Preparing method for conductive composite bronze powder and composite bronze conductive sizing agent |
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| JPH04323309A (en) * | 1991-04-12 | 1992-11-12 | Daido Steel Co Ltd | Production of fine metal powder |
| JPH0978619A (en) * | 1995-09-11 | 1997-03-25 | Takiron Co Ltd | Structure for fixing lid to lid support frame |
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1997
- 1997-11-17 CN CN97121904A patent/CN1060982C/en not_active Expired - Lifetime
Patent Citations (2)
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|---|---|---|---|---|
| JPH04323309A (en) * | 1991-04-12 | 1992-11-12 | Daido Steel Co Ltd | Production of fine metal powder |
| JPH0978619A (en) * | 1995-09-11 | 1997-03-25 | Takiron Co Ltd | Structure for fixing lid to lid support frame |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300381C (en) * | 2003-06-16 | 2007-02-14 | 昆明理工恒达科技有限公司 | Preparing method for conductive composite bronze powder and composite bronze conductive sizing agent |
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| CN1217960A (en) | 1999-06-02 |
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