CN1060703C - Method for preparing nanometre metal powder - Google Patents
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Abstract
The present invention relates to a process for preparing metal powder by a chemical method. Metal salts are used as the raw material, zinc powder is used as a reducing agent for displacement, and ammonia water is used as a complexing agent; an ammonia complexing ionized water solution of the metal salts containing a dispersing agent is uniformly mixed with a zinc powder suspension uniformly dispersed, and the stirring is continuously carried out, until the reaction is completed; the ammonia water is used for washing a metal powder precipitate, and the metal powder precipitate is then washed with water. The redundant zinc powder is dissolved by an acid solution or an alkali solution, and the metal powder is washed with water until the metal powder is neutral. The nanometer-scale metal powder produced by using the process of the present invention has the advantages of narrow distribution range of particle sizes, high purity and no inclusion (such as oxides, chlorides, etc.); the process of the present invention has the advantages of high recovery rate of the metal, and simple process; the process of the present invention can be used for large-scale production.
Description
The present invention relates to prepare the method for metal powder, more specifically say so with the method for complexing displacement reduction method for preparing nanometer level metal powder with chemical method.
The research of nano level superfine powder is one of focus of present material scientific research.The material that nanometre metal powder forms has accounted for sizable ratio because its crystallite dimension, is positioned at the atom on crystal boundary and surface less than 100nm in the crystal, so all different with the material of non-nano metal powder formation from mechanical property to electricity, magnetic, optical property.It has better performance, compares with the agglomerated material of general micron order crystal grain, and the agglomerated material of nanometer-size die can reach higher intensity and density, and ductility is good.For example, the common copper product of the thermal conductivity ratio of the copper material that the nano level metal copper powder forms is high 100 times, can be used in the high-efficiency radiator, is used for the burn of preventing laser weapon.Nanoscale copper powder, silver powder can be used for part and replace noble metal to make catalyst in petrochemical industry, can quicken the decomposition of long hydrocarbon chain.In addition, because the specific surface of nanometre metal powder is big, activity is very strong, oxidation takes place in air easily, in rocket-propelled solid fuel, can add the nanoscale copper powder or other nanometre metal powders are made combustion adjuvant, can strengthen solid-fuelled efficiency of combustion, improve combustion speed.Obtained using widely in each high-tech area just because of nanometre metal powder, the researcher of countries in the world has carried out number of research projects to the technology of making nanometre metal powder.
H.Gleiter [in Deformation of polycrystals Mechanism andMicrostructures edited by N.Hansen etal (Riso National Laboratory, Roislcilde 1981, P16)] at first be equipped with nano material with the evaporation-condensation legal system.The technology that has occurred various preparation nano materials over past ten years again.Except that the evaporation-condensation method, also have ion sputtering method, radio frequency and microwave plasma CVD method, chemical methods such as physical method such as LASER HEAT decomposition method, amorphous band annealing method, high-energy ball milling and collosol and gel.But, the nano material amount that above-mentioned physical method is prepared at every turn is few, and apparatus expensive, product cost is too high, further investigation and application have been influenced to its performance, for example mechanical property research just needs relatively large sample, and therefore preparing the feather weight nano material with the low technology of the simple cost of technology has become at present nano materials research and key in application both at home and abroad.Though the plasma method of dusting can be produced more metal nano powder, distribution of particles is inhomogeneous, has thick particle to exist.
It is high-quality that purpose of the present invention just is to work out preparation, even particle size distribution, and the method for the nanometre metal powder of no thick particle, and make that the technology of manufacturing nanometre metal powder is simple, low cost product.
The preparation method of a kind of nanometre metal powder of the present invention, its step comprises:
(1) will place container as the slaine of raw material, add an amount of water and ammoniacal liquor, mix, generate the metal ammonium complex ion aqueous solution, adding dispersant again mixes, wherein, amount of metal is 1 with the weight ratio of the dispersion dosage that added in the slaine: 0.1-2.0, with the mol ratio of the ammonia amount that is added be 1: 2.0-10;
(2) will place container as the zinc powder of displacement reducing agent, and add entry and stir, wherein the mol ratio of amount of metal and the amount of the zinc powder that added is 1 in the slaine: 2.0-8.0;
(3) the uniform zinc powder suspension of dispersed with stirring is placed cold bath,, continue to be stirred to the reduction displacement reaction and finish under agitation with metal ammonium complex ion aqueous solution;
(4) static clarification, the tipping supernatant with the ammonia scrubbing precipitation, after washing with water, is removed zinc powder with the aqueous solution dissolving of acid or alkali again, washes with water to neutrality, uses absolute ethanol washing, vacuum freeze drying.
The nanometre metal powder of being produced is wherein a kind of of silver, copper, nickel, cobalt powder.Used cold water is good with 0 °～40 ℃ when cooling off in the cold bath.The metal ammonium complex ion aqueous solution was advisable to continue to stir with after zinc powder suspension mixes in 0.5～20 hour.The rate request that stirs is not strict, but is good with the fast speeds stirring.Displacement reaction is finished, and static clarification after the tipping supernatant, with the ammonia scrubbing metal powder precipitation of 0.5-5 mol 2-5 time, washes 2-5 time with water for well again.It is wherein a kind of of hydrochloric acid, sulfuric acid, acetic acid that the used acid of zinc powder is removed in dissolving, removes zinc powder for well with hydrochloric acid, the acetic acid of 0.1～6 mol, 0.05～3 mol sulfuric acid of 0.1～6 mol again.Wherein a kind of of the aqueous solution that the used alkali of zinc powder is NaOH, potassium hydroxide, lithium hydroxide removed in dissolving.Again with wherein a kind of for well of the NaOH of 1-6 mol, potassium hydroxide, lithium hydroxide.After zinc powder is removed in dissolving, wash with water, filter, be filtered into good with the glass sand core funnel usually during filtration to neutrality.Precipitation is washed with water to neutrality, generally need wash with water 4-10 time.Use absolute ethanol washing product 2-4 time again, take advantage of wet bottling, vacuum freeze drying, sealing is preserved.
Used water is ion exchange water, water such as distilled water.Used dispersant is polyvinyl alcohol (polyethylene glycol), wherein a kind of of emulsification OP (Triton X-100), tritonX-100 (polyoxyethylene alkyl ether).The granularity of used zinc powder is below 100 microns, with 5～100 microns for well.Metal powders such as magnesium powder, iron powder can replace metal zinc as the displacement reducing agent.
If preparation nanometer-level silver metal powder used raw material silver salt is silver nitrate, silver sulfate, silver acetate even silver chlorate a kind of silver salt wherein of newly being precipitated out.
If the used raw material mantoquita of preparation nanosized copper metal powder is copper chloride, copper sulphate, stannous chloride, copper nitrate a kind of mantoquita wherein.
If the used raw material nickel salt of preparation nanoscale nickel metal powder is nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate a kind of nickel salt wherein.
If the used raw material cobalt salt of preparation nanometre grade cobalt metal powder is wherein a kind of cobalt salt of cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate.
Because metal nickel powder, metal cobalt powder dissolve in acid, so dissolving when removing zinc powder with the aqueous solution a kind of aqueous solution wherein of the NaOH of 1～6 mol, potassium hydroxide, lithium hydroxide for well, especially better with 1-6 mol sodium hydrate aqueous solution.
The displacement reduction process on the zinc particle surface, the argent that is reduced, copper, nickel, cobalt a kind of metal and zinc has wherein been formed a microcell battery, zinc is negative pole, the argent of being gone back, copper, cobalt, nickel are for anodal, silver, copper, cobalt, nickel ion begin nucleation on the activation point of zinc powder, may form the nuclear of several silver, copper, cobalt, nickel a kind of metal wherein on a zinc powder.These metal core are constantly grown up in the displacement reduction process, form the superfine nano metal powder.In the displacement reduction process,, add ammoniacal liquor for the speed of controlling silver, copper, cobalt, nickle atom nucleation and too fast the growing up of nuclear.Because it is stable strong that these metal ions and ammino close the metal network ammonium ion of formation, may be controlled to the speed of nuclear and the speed that nuclear is grown up.In the complex system of these metal ions and ammonia, the concentration of ammonia is an important factor in the displacement reduction process, and the concentration of ammoniacal liquor is too low, can not play complexing; The concentration of ammoniacal liquor is too high, and the stability of metal ammino-complex increases, and is difficult for by the displacement reduction.And in the displacement reduction process, can produce the molten phenomenon of zinc.For the displacement reduction process is carried out smoothly, the Total Water that is added in by the complex system of the metal ion of displacement reduction and ammonia is 1: 2.6～18 to be good with the volume ratio of the Total Water of the commercially available concentrated ammonia liquor amount that adds and adding.
Because general redox reaction all is exothermic reaction, the temperature rising for fear of reaction solution causes grain growth, so cool off with cold water in cold bath.
Because added excessive zinc powder in displacement reduction reaction process, reaction is finished still residual zinc powder in the afterreaction container, residual zinc powder can dissolve with acid or alkali to be removed, till not producing hydrogen.When the dissolving zinc powder, taken away heat, in the process of dissolving zinc powder, can cool off without cold water owing to there is a large amount of hydrogen to overflow.
The preparation method's of nanometre metal powder of the present invention advantage just is:
1. because method of the present invention has adopted the complexing displacement method, can suitably control the granular size of nanometre metal powder and the size of its crystal grain, nano level metal powder particles and the crystallite dimension prepared are little, narrow distribution range, the nanometre metal powder purity height that its crystal grain becomes to heap shape, produce, the field trash of oxide-free, chloride etc.
2. one step of collection of method reduction of the present invention and precipitation finishes, and does not generate colloidal solution, does not need to add anti-charge ion coagulating agent, and is obvious with the water sedimentation separation, is convenient to washing, is convenient to separate with aqueous phase solution.Method of the present invention does not need expensive especially main equipment again, invest low, instant effect, the rate of recovery height of metal, product with low cost.
3. method of the present invention is simple, and technological process is short, easy operating.
4. can produce the feather weight nanometre metal powder with method of the present invention, can produce relatively largely, with the nanometre metal powder that this law is produced, the metal block material specific density height that under pressure, directly suppresses.
Nano-scale silver powder, copper powder, nickel powder, the cobalt powder prepared with the displacement reducing process prove noresidue zinc, metal oxide and chloride through X-ray diffraction, X-ray fluorescent and chemical analysis.
Determined the granularity of silver powder, copper powder, nickel powder, cobalt powder with X-ray diffracted ray conformal analysis.X-ray diffracted ray conformal analysis is to calculate grain size according to the physics broadening of diffracted ray.For example copper selects for use (111) diffracted ray of copper to do linear analysis.The copper powder crystallite dimension that calculates with this method is 14.5 nanometers.
The granularity of observing silver powder, copper powder, nickel powder, cobalt powder with high resolution analysis type transmission electron microscope, also prove through electronic microscope photos do not have silver, copper, nickel, cobalt/cobalt oxide and chloride exist.
X light diffracting analysis adopts APD-10 X-ray diffractometer, and sweep speed is 4 °/minute, to determine phase constituent and crystallite dimension, uses the CuK alpha ray when measuring copper powder.
The microphoto of Fig. 1 nanoscale copper powder
With the take pictures granularity of copper powder of JEM-2000FX electron microscope observation, multiplication factor * 50K.
Because the easy oxidation of superfine cupper powder, be dispersed on the copper mesh of carbon film when the nanoscale copper powder after, be kept in the argon gas till inserting the Electronic Speculum vacuum.The observation of transmission electron microscope as shown in Figure 1.As can be seen from Figure 1 the size of copper particle is substantially about 20 nanometers.
The statistical distribution of Fig. 2 nanosized copper powder particles size
The nanosized copper particle has been carried out the mensuration of statistical distribution, totally 400 particles in the selected electromicroscopic photograph zone, its size distribution is as shown in Figure 2.As can be seen from Figure 2 its particle size distribution is very narrow, does not have the particle greater than 40 nanometers.Distribution of particles more than 80% is between 15～25 nanometers.Its method is after taking pictures with the JEM-2000FX electron microscope earlier, to amplify 4 times of sizes of measuring each particle again with the magnifying glass that scale is arranged, and the size of adding up about 400 particles is made the statistical Butut.Among the figure, abscissa is nanometer (nm), the ordinate granule number.
Fig. 3 nanoscale nickel powder particle microphoto
Take pictures multiplication factor * 50K with the JEM-2000FX electron microscope.
The nano-scale silver powder of preparing, copper powder, nickel powder, cobalt powder do not have agglomeration, and the color of copper powder is a bronzing, and silver powder is taupe, and cobalt powder, nickel powder are aterrimus.These nano-scale silver powders, copper powder, nickel powder, cobalt powder surface-active are very big, the oxidation rapidly under the situation of no argon shield that has, and heating has the possibility of blast.Thereby must be placed on vacuum or in argon gas atmosphere, preserve.So the sample of making X light diffracting analysis is to analyze on the X-ray diffractometer after protective atmosphere depresses to fine and close block sample.
With following non-limiting examples technology of the present invention is further described, will helps the further understanding to the present invention and advantage thereof, and not as a limitation of the invention, protection scope of the present invention is decided by claims.
Embodiment 1
With the stannous chloride is that raw material (commercially available, as to analyze pure) places 2500 milliliters beaker, adds an amount of water and ammoniacal liquor.The ammonia vol that is added by the amount of copper in the stannous chloride with adds the amount of ammonia mol ratio be 1: 4, make stannous chloride dissolve the generation ammoniacal copper complex ion aqueous solution, used ammoniacal liquor is commercially available analytically pure ammoniacal liquor.The dispersant that adds is commercial polyethylene alcohol (polyethylene glycol), mixes, and the amount of the polyvinyl alcohol that is added is 1: 0.3 by the weight ratio of the amount of copper in the stannous chloride and the amount of the polyvinyl alcohol that is added.Will be as the zinc powder of displacement reducing agent, it is even to place beaker to add the entry dispersed with stirring.The zinc powder that adds is that commercially available analysis is pure, and its granularity is below 20 microns, and the amount of the zinc powder that is added is 1: 2 by the mol ratio of the copper amount in the stannous chloride and the zinc powder amount that is added.With the uniform zinc powder suspension of dispersed with stirring in cold bath under agitation with the ammoniacal copper complex ion aqueous solution, continue to be stirred to the aqueous solution colourless till, make displacement reaction complete.Leave standstill clarification, the tipping supernatant.The nanoscale copper powder precipitation that generates with the ammonia scrubbing of 0.5 mol 3 times, water washing is 3 times again.With concentration is that unnecessary zinc powder is removed in hydrochloric acid (with the preparation of the commercially available analysis pure hydrochloric acid) dissolving of 1 mol, produces until no longer including bubble hydrogen.The tipping supernatant washes with water to neutrality, filters with G3 flint glass F sand core funnel, uses absolute ethanol washing 2 times, taking advantage of wet bottling, vacuum freeze drying, and sealing is preserved.Used water is secondary ion exchange process deionized water.The rate of recovery of metallic copper is 94.1%.
Embodiment 2
Its method of operating is substantially the same manner as Example 1, and only different is is raw material with the copper chloride.The ammonia vol that is added by the amount of copper in the copper chloride with add the amount of ammonia mol ratio be 1: 6, the amount of the polyethylene of dispersing agent alcohol that is added is 1: 0.5 by the weight ratio of the amount of the amount of copper in the copper chloride and the polyvinyl alcohol that added.The amount of the zinc powder that is added is 1: 5 by the mol ratio of the copper amount in the copper chloride and the zinc powder amount that added, and its granularity of the zinc powder that is added is below 50 microns.The zinc powder suspension that stirs is descended and the ammoniacal copper complex ion aqueous solution in stirring in 20 ℃ cold water, continue to stir 0.7 hour, complete to displacement reaction, static clarification, the tipping supernatant, ammonia scrubbing with concentration 1 mol precipitates 2 times, washing with water 4 times, is that the dissolving with hydrochloric acid of 2 mol is removed unnecessary zinc powder with concentration again, produces until no longer including hydrogen gas bubbles, zinc is removed totally, the tipping supernatant washes with water to neutrality, filter, use absolute ethanol washing 3 times, taking advantage of wet bottling, vacuum freeze drying, applying argon gas sealing preservation again after vacuum or the vacuum.The rate of recovery of metallic copper is 95%.The microphoto of products obtained therefrom nanoscale copper powder as shown in Figure 1, the statistical distribution of its particle size as shown in Figure 2, the distribution of particles more than 80% is between the 15-25 nanometer, the nanoscale copper powder of preparing is spherical in shape, no agglomeration, color are bronzing, and the largest particles is no more than 40 nanometers.
Embodiment 3
Its method of operating is substantially the same manner as Example 1, the ammonia vol that only different is is added by the amount of copper in the stannous chloride with add the ammonia amount mol ratio be 1: 5; The dispersant that is added is a polyoxyethylene nonylphenol ether, and the amount of the polyoxyethylene nonylphenol ether that is added is 1: 1 by the weight ratio of the amount of copper in the stannous chloride and the amount of the emulsifying agent 0P that is added.The amount of the zinc powder that is added, by the amount of copper in the stannous chloride with add the zinc powder amount mol ratio be 1: 3.The granularity of the zinc powder that is added is below 50 microns.In 15 ℃ cold water, continue to stir 2 hours.Remove unnecessary zinc powder with the dissolving with hydrochloric acid of 0.3 mol.The rate of recovery of metallic copper is 95%.
Embodiment 4
With the silver nitrate is that raw material (commercially available, as to analyze pure) places 2500 milliliters beaker, adds an amount of water and ammoniacal liquor.The ammonia vol that is added is 1: 4 by the mol ratio of the amount of silver in the silver nitrate and the ammonia amount that added, makes the silver nitrate dissolving generate the aqueous solution of silver ammino ion.Used ammoniacal liquor is commercially available analytically pure ammoniacal liquor.The dispersant that adds is a commercial polyethylene alcohol, mixes.The amount of the polyvinyl alcohol that is added is 1: 0.2 by the weight ratio of the amount of silver in the silver nitrate and the amount of the polyvinyl alcohol that added, will place beaker as the zinc powder of displacement reducing agent, and it is even to add the entry dispersed with stirring.The zinc powder that adds is that commercially available analysis is pure, and its granularity is below 50 microns, and the amount of the zinc powder that is added is 1: 2.5 by the mol ratio of the amount of the silver in the silver nitrate and the zinc powder amount that is added.In by the complex system of the metal ion of displacement reduction and ammonia, the Total Water that is added is 1: 5 for commercially available ammonia vol that adds and the volume ratio that adds Total Water.The uniform zinc powder suspension of dispersed with stirring in 10 ℃ cold bath, under agitation with the silver ammino ion aqueous solution, is continued to stir 0.5 hour, make displacement reaction carry out fully, leave standstill clarification, tipping supernatant.The nano-scale silver powder that generates with the ammonia scrubbing of 0.7 mol 5 times dissolves and removes unnecessary zinc powder with the hydrochloric acid (with commercially available, analytically pure hydrochloric acid is prepared) of 3 mol, produce until no longer including bubble hydrogen, the tipping supernatant washes with water to neutrality, filters with G3 flint glass F sand core funnel, with absolute ethanol washing 2 times, take advantage of wet bottling, vacuum freeze drying, sealing is preserved, used water is secondary ion exchange process deionized water, and the rate of recovery of argent is 95.4%.
Embodiment 5
Its method of operating is substantially the same manner as Example 4, and only different is with the silver chlorate that newly is settled out is raw material, the ammonia vol that is added by the amount in the silver chlorate with add the ammonia amount mol ratio be 1: 6.The dispersant that adds is tritonX-100, the amount of the zinc powder that is added, by the amount of silver in the silver chlorate with add zinc powder and add the amount of zinc powder mol ratio be 1: 3.The rate of recovery of argent is 95%.
Embodiment 6
With the nickel chloride is that raw material (commercially available, as to analyze pure) places 2500 milliliters beaker, adds an amount of water and ammoniacal liquor, and the ammonia vol that is added is 1: 4 by nickel amount in the nickel chloride with the mol ratio that institute adds the amount of ammonia, makes nickel chloride dissolve the generation nickel-ammonia complex ion aqueous solution.Used ammoniacal liquor is the pure ammoniacal liquor of commercially available analysis.The dispersant that adds is a commercial polyethylene alcohol, mixes, and the amount of the polyvinyl alcohol that is added is 1: 0.15 by the weight ratio of the amount of nickel in the nickel chloride and the amount of the polyvinyl alcohol that is added.Will be as the zinc powder of displacement reducing agent, place beaker, it is even to add the entry dispersed with stirring, and the zinc powder of adding is that commercially available analysis is pure, its granularity is below 30 microns, and the amount of the zinc powder that is added is 1: 2.7 by the mol ratio of the nickel amount in the nickel chloride and the zinc powder amount that is added.In by the complex system of the metal ion of displacement reduction and ammonia, the Total Water that is added is 1: 6 for commercially available ammonia vol that adds and the volume ratio that adds Total Water.The uniform zinc powder suspension of dispersed with stirring in 25 ℃ cold bath, under agitation with the nickel-ammonia complex ion aqueous solution, is continued to stir 6 hours, displacement reaction is carried out fully.Leave standstill clarification, the tipping supernatant.The nanoscale nickel powder that generates with the ammonia scrubbing of 4 mol 4 times, wash with water 4 times, change in the vinyon cup, unnecessary zinc powder is removed in sodium hydroxide solution dissolving with 1.5 mol, and the tipping supernatant is washed with water to neutrality (washing with water 4 times), filter with G3 flint glass F sand core funnel, with absolute ethanol washing 3 times, take advantage of wet bottling vacuum freeze drying, sealing is preserved.Used water is secondary ion exchange process deionized water.The rate of recovery of metallic nickel is 80%.The microphoto of the product nano level metal nickel powder that is generated as shown in Figure 3.
Embodiment 7
Its method of operating is substantially the same manner as Example 6, and only different is with nickelous sulfate NiSO
46H
2O is a raw material, the amount of the ammoniacal liquor that is added, by the nickel amount in the nickelous sulfate with add the amount of ammonia mol ratio be 1: 6.The amount of the zinc powder that is added is 1: 3 by the mol ratio of the nickel amount in the nickelous sulfate and the amount of the zinc powder that added.The Total Water that is added is commercially available ammonia vol and the volume ratio that adds Total Water is 1: 8, continues to stir 8 hours, and the nanoscale nickel powder that generates with the ammonia spirit washing of 6 mol 4 times dissolves with the sodium hydroxide solution of 3 mol and to remove unnecessary zinc powder.The rate of recovery of metal nickel powder is 81%.
Embodiment 8
Its method of operating is substantially the same manner as Example 6, and only different is is raw material with the cobalt chloride, and the rate of recovery of metallic cobalt is 80%.
Claims (17)
1. the preparation method of a nanometre metal powder, its step comprises:
(1) will place container as the slaine of raw material, add an amount of water and ammoniacal liquor, mix, generate the metal ammonium complex ion aqueous solution, adding dispersant again mixes, wherein, amount of metal is 1 with the weight ratio of the dispersion dosage that added in the slaine: 0.1-2.0, with the mol ratio of the ammonia amount that is added be 1: 2.0-10;
(2) will place container as the zinc powder of displacement reducing agent, and add entry and stir, wherein the mol ratio of amount of metal and the amount of the zinc powder that added is 1 in the slaine: 2.0-8.0;
(3) the uniform zinc powder suspension of dispersed with stirring is placed cold bath,, continue to be stirred to the reduction displacement reaction and finish under agitation with metal ammonium complex ion aqueous solution;
(4) static clarification, the tipping supernatant with the ammonia scrubbing precipitation, after washing with water, is removed zinc powder with the aqueous solution dissolving of acid or alkali again, washes with water to neutrality, uses absolute ethanol washing, vacuum freeze drying.
2. according to the preparation method of a kind of nano level metal of claim 1, it is characterized in that said nanoscale powder is wherein a kind of of silver, copper, nickel, cobalt powder.
3. according to the preparation method of a kind of nanometre metal powder of claim 1, it is characterized in that the cold water in the cold bath is 0 °～40 ℃.
4. according to the preparation method of a kind of nanometre metal powder of claim 1, it is characterized in that, continue to stir 0.5～20 hour.
5. according to the preparation method of a kind of nanometre metal powder of claim 1, it is characterized in that, with the ammonia scrubbing metal powder precipitation of 0.5～5 mol.
6. according to the preparation method of a kind of nanometre metal powder of claim 5, it is characterized in that, behind ammonia scrubbing, wash with water 2-5 time.
7. according to the preparation method of a kind of nanometre metal powder of claim 1 or 6, it is characterized in that with the unnecessary zinc powder of acid dissolving, used acid is wherein a kind of of hydrochloric acid, sulfuric acid, acetic acid.
8. according to the preparation method of a kind of nanometre metal powder of claim 7, it is characterized in that the concentration of hydrochloric acid, acetic acid is 0.2～6 mol, sulfuric acid is 0.05～3 mol.
9. according to the preparation method of a kind of nanometre metal powder of claim 1 or 6, it is characterized in that with the unnecessary zinc powder of alkali dissolving, used alkali is wherein a kind of of NaOH, potassium hydroxide, lithium hydroxide.
10. according to the preparation method of a kind of nanometre metal powder of claim 9, it is characterized in that the concentration of NaOH, potassium hydroxide, lithium hydroxide is the 1-6 mol.
11. the preparation method according to a kind of nanometre metal powder of claim 1 is characterized in that dispersant is polyvinyl alcohol, polyoxyethylene nonylphenol ether, wherein a kind of of polyoxyethylene alkyl ether.
12. the preparation method according to a kind of nanometre metal powder of claim 1 is characterized in that the granularity of zinc powder is below 100 microns.
13. the preparation method according to a kind of nanometre metal powder of claim 1 is characterized in that said slaine is a silver salt, wherein a kind of of the silver chlorate that said silver salt is silver nitrate, silver sulfate, silver acetate, newly be precipitated out.
14. the preparation method according to a kind of nanometre metal powder of claim 1 is characterized in that said slaine is a mantoquita, said mantoquita is wherein a kind of of copper chloride, copper sulphate, stannous chloride, copper nitrate.
15. the preparation method according to a kind of nanometre metal powder of claim 1 is characterized in that said slaine is a nickel salt, said nickel salt is wherein a kind of of nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate.
16. the preparation method according to a kind of nanometre metal powder of claim 1 is characterized in that said slaine is a cobalt salt, said cobalt salt is wherein a kind of of cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate.
17. preparation method according to a kind of nanometre metal powder of claim 1, it is characterized in that the Total Water that is added is 1: 2.6～18 with the volume ratio of the Total Water of the commercially available concentrated ammonia liquor amount of adding and adding in by the complex system of the metal ion of displacement reduction and ammonia.
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| CN115519115B (en) * | 2022-09-26 | 2024-04-30 | 陕西师范大学 | Method for preparing silver chloride-silver composite structure micro array by laser irradiation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072120A (en) * | 1991-10-16 | 1993-05-19 | E·I·内穆尔杜邦公司 | Make the method for finely divided particles of silver metals |
| CN1120987A (en) * | 1994-10-20 | 1996-04-24 | 中国科学院山西煤炭化学研究所 | Method of preparing composite superfine powder with metal surfactant by phase transfer |
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1996
- 1996-05-30 CN CN96105280A patent/CN1060703C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072120A (en) * | 1991-10-16 | 1993-05-19 | E·I·内穆尔杜邦公司 | Make the method for finely divided particles of silver metals |
| CN1120987A (en) * | 1994-10-20 | 1996-04-24 | 中国科学院山西煤炭化学研究所 | Method of preparing composite superfine powder with metal surfactant by phase transfer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7785392B2 (en) | 2006-07-06 | 2010-08-31 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing metal nanoparticles |
| CN101100002B (en) * | 2006-07-06 | 2010-12-08 | 三星电机株式会社 | Method for producing metal nano granule |
| CN101347843B (en) * | 2008-09-12 | 2011-06-08 | 安徽工业大学 | Method for preparing metallic nickel nano powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1171992A (en) | 1998-02-04 |
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