CN107617739B - A kind of preparation method of tungsten copper argentum composite powder body - Google Patents
A kind of preparation method of tungsten copper argentum composite powder body Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of tungsten copper argentum composite powder body, it is impregnated including tungsten powder to be placed in wetting agent, tungsten powder is placed in copper facing in the copper plating solution of alkalinity afterwards, it is the alkaline complex copper ion solution formed by soluble copper salt and copper ion complexing agent in copper plating solution, reducing agent solution is added in copper facing tungsten powder afterwards, stirring makes copper facing tungsten powder be uniformly dispersed, silver ion complexation agent is added in silver salt solution under stirring condition, complexing silver salt solution is made, complexing silver salt solution is added in the mixture of copper facing tungsten powder and reducing agent, 30~90min of reduction reaction occurs, tungsten copper argentum composite powder body is made, the resulting tungsten copper argentum composite powder body of the method for the present invention is silver-plated smooth with copper facing and uniformity is good, coating is tightly combined, the features such as with high purity, and it can be carried out large-scale production, it can be widely applied to middle/high-voltage electrical appliance, it is logical The fields such as news, aviation, machinery, electronics, metallurgy, space flight and military project.
Description
Technical field
The present invention relates to a kind of preparation method of composite granule more particularly to a kind of preparation sides of tungsten copper argentum composite powder body
Method belongs to chemical surface treatment technical field.
Background technique
Tungsten powder has the features such as fusing point is high, and density is big, and hardness is high, and saturated vapor forces down, and thermal expansion coefficient is small, especially tungsten
Copper silver composite material has outstanding arc resistant ablation, resistance fusion welding and good conductive, thermal conductivity, is widely used in mesohigh
The fields such as electric appliance, communication, aviation, machinery, electronics, metallurgy, space flight and military project.Tungsten copper silver composite material is because having anti-high pressure, resistance to
The performances such as electric ablation, high rigidity and in terms of being used in high-voltage electric contact and high-voltage capacitor, and exist as weldering electrode material
Space industry is applied.Electronic Encapsulating Technology is the important component of modern electronics industry, chip and base in encapsulation process
Interconnection technique level between plate, chip and circuit limits electronic product to miniaturization, portability development.In recent years, electronics
The protrusion of industry integrated circuit is that the tungsten copper silver composite material for having excellent encapsulation performance brings the opportunity to develop of a new round.
Tungsten copper argentum composite powder body has wetability between uniform small grains, electric-conductivity heat-conductivity high, large specific surface area, metal good
Many advantages, such as, it is extremely advantageous to subsequent molding and sintering process in field of metallurgy.In recent years for ultra-fine uniform tungsten copper silver
Composite granule produces research intimately.Currently prepare tungsten copper argentum composite powder body method it is numerous, mainly include mechanical alloying method,
Sol-gel method, spray drying process, electroless plating method etc..
Machine-alloying has technique flexibly simple, is not necessarily to hot environment, low energy consumption, and yield is big, and the composite powder worn into is equal
It is even tiny, but repeatedly grinding will increase the iron content in composite powder for a long time, and this will affect the conductive hot property of composite granule.
The advantages such as sol-gel method has reaction temperature low, and reaction controllability is high, and out-phase side reaction is few, the powder prepared have pure
Degree is high, the advantages such as chemical uniformity is good, and structure is single tiny, and heat treatment temperature is low.But there are long preparation period, costs for the technique
The problems such as height, volume production is difficult.Spray drying process each process is easily controllable, and the oxide precursor after dry nebulization is generally in ball
Shape ghost shape, product impurity is low, is suitble to large-scale industrial production, but process is more, and energy consumption is high.
Summary of the invention
The present invention is directed to the existing machine-alloying for preparing tungsten copper argentum composite powder body, sol-gel method, spray drying process
Existing deficiency provides a kind of preparation method of tungsten copper argentum composite powder body.
The technical scheme to solve the above technical problems is that
A kind of preparation method of tungsten copper argentum composite powder body, includes the following steps:
1) tungsten powder is placed in wetting agent and is impregnated, rinsed after taking-up using deionized water；
2) the resulting tungsten powder of step 1) is placed in copper plating solution, is stirred, while controlled at 50~60 DEG C, reaction 10
Rinsed after~20min using deionized water, be centrifugated out copper facing tungsten powder, wherein the pH of copper plating solution control for 11~
14, the copper plating solution is the aqueous solution that the mixing solute being made of soluble copper salt, copper ion complexing agent is formed, control copper with
The mass ratio of tungsten is 0.10~0.15；
3) reducing agent solution is added in the resulting copper facing tungsten powder of step 2), stirring makes it be uniformly dispersed；
4) silver ion complexation agent is added in silver salt solution under stirring condition and complexing silver salt solution is made, after by complex silver
Salting liquid is added in the resulting mixture of step 3), and 30~90min of reduction reaction occurs, and it is 5~15wt% that silver content, which is made,
Tungsten copper argentum composite powder body；
5) the resulting tungsten copper argentum composite powder body of step 4) is washed, it is rear to be centrifugated；Vacuum drying to get.
Based on the above technical solution, the present invention can also be improved as follows.
Further, silver ion complexation agent described in step 4) be trisodium citrate, it is triethanolamine, any one in imidazoles
The mass ratio of kind or a variety of mixtures, silver salt and the complexing agent is 1:(1~5).
Further, the silver salt refers to silver nitrate, any one in silver acetate.
Further, wetting agent described in step 1) is ethyl alcohol, isopropanol, the mixing of any one or more in acetone
The mass ratio of object, tungsten powder and the wetting agent is (1~10): 1.
Further, copper ion complexing agent described in step 2) be EDTA, any one in trisodium citrate, it is described can
Dissolubility mantoquita refers to copper nitrate, copper sulphate, any one in copper chloride.
Further, the mass ratio of soluble copper salt described in step 2) and copper ion complexing agent is 1:(1~2.5).
Further, reducing agent described in step 3) is formaldehyde, glucose, hydrazine sulfate, any one in sodium potassium tartrate tetrahydrate
Or a variety of mixtures, the mass ratio of tungsten powder and the reducing agent are (1~10): 1.
Further, vacuum drying temperature is 80~100 DEG C in step 5).
The beneficial effects of the present invention are:
1) method provided by the invention uses electronation technology, and the pre-treating technology of tungsten powder impregnates technology using wetting agent
Instead of traditional roughening, sensitization, activating technology, using novel complexing agent prescription, in the reduction process of silver ion, in copper powder
Surface forms galactic nucleus and grows up, and forms the smooth silver layer of continuous dense uniform, at low cost, it is easy to accomplish large-scale production；
2) the resulting tungsten copper argentum composite powder body of the method for the present invention have copper facing is silver-plated smooth and uniformity is good, coating combine it is tight
The features such as close, with high purity, and can be carried out large-scale production, it can be widely applied to middle/high-voltage electrical appliance, communication, aviation, machinery, electricity
The fields such as son, metallurgy, space flight and military project.
Detailed description of the invention
Fig. 1 is 400 times of magnified sweep electromicroscopic photographs of 1 gained tungsten copper argentum composite powder body of the embodiment of the present invention；
Fig. 2 is 5000 times of magnified sweep electromicroscopic photographs of 1 gained tungsten copper argentum composite powder body of the embodiment of the present invention；
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
A kind of preparation method of tungsten copper argentum composite powder body, includes the following steps:
1) it takes tungsten powder 1kg to be added in the wetting agent ethyl alcohol of 250ml to impregnate 1 hour, be rinsed after taking-up using deionized water；
2) then tungsten powder is added in the copper plating bath that volume is 40L, the content of each substance in copper plating bath are as follows: copper nitrate
10g/L, EDTA 25g/L, using NaOH adjust copper plating bath pH be 11~12, controlled at 60 DEG C stir 10 minutes, then
It is rinsed using deionized water, and copper facing tungsten powder is isolated using centrifuge；
3) it by formalin 120mL, deionized water 10kg, is added in copper facing tungsten powder obtained above, and high speed machine stirs
It mixes, copper facing tungsten powder is made to be uniformly dispersed；
4) under agitation, trisodium citrate 220g is added in the aqueous solution of 1000ml of the 80g containing silver nitrate, is made
At complexing silver salt solution, silver salt solution then will be complexed, be added in the copper facing tungsten powder containing reducing agent, and react 30 minutes, be made
5% tungsten copper argentum composite powder body of silver content；
5) the resulting composite granule of step 4) is centrifugated, is placed at 80 DEG C and is dried in vacuo to get finished product.
Embodiment 2:
A kind of preparation method of tungsten copper argentum composite powder body, includes the following steps:
1) it takes tungsten powder 1kg to be added in the wetting agent isopropanol of 130ml to impregnate 1 hour, be rushed after taking-up using deionized water
It washes；
2) then tungsten powder is added in the copper plating bath that volume is 40L, the content of each substance in copper plating bath are as follows: copper chloride
10g/L, EDTA 10g/L, using NaOH adjust copper plating bath pH be 11~12, controlled at 50 DEG C stir 15 minutes, then
It is rinsed using deionized water, and copper facing tungsten powder is isolated using centrifuge；
3) it by sodium potassium tartrate tetrahydrate 120g, deionized water 10kg, is added in copper facing tungsten powder obtained above, and high speed machine stirs
It mixes, copper facing tungsten powder is made to be uniformly dispersed；
4) under agitation, triethanolamine 850g is added in the 1000ml aqueous solution of the 170g containing silver nitrate, is made
Silver salt solution is complexed, then complexing silver salt solution is added in the copper facing tungsten powder containing reducing agent, reacts 60 minutes, silver is made and contains
Measure 10% tungsten copper argentum composite powder body；
5) the resulting composite granule of step 4) is centrifugated, is placed at 80 DEG C and is dried in vacuo to get finished product.
Embodiment 3:
A kind of preparation method of tungsten copper argentum composite powder body, includes the following steps:
1) it takes tungsten powder 1kg to be added in the wetting agent acetone of 1250ml to impregnate 1 hour, be rushed after taking-up using deionized water
It washes；
2) then tungsten powder is added in the copper plating bath that volume is 40L, the content of each substance in copper plating bath are as follows: copper sulphate
10g/L, trisodium citrate 15g/L are 12~14 using the pH that NaOH adjusts copper plating bath, and control temperature 60 C stirs 20 minutes,
Then it is rinsed using deionized water, and copper facing tungsten powder is isolated using centrifuge；
3) it by hydrazine sulfate 200g, deionized water 10Kg, is added in copper facing tungsten powder obtained above, and high speed machine stirs,
Copper facing tungsten powder is set to be uniformly dispersed；
4) trisodium citrate 240g, triethanolamine 200g under agitation, are added to the 240g's containing silver nitrate
In 1000ml aqueous solution, complexing silver salt solution is made, silver salt solution then will be complexed, is added to the copper facing tungsten powder containing reducing agent
In, it reacts 90 minutes, 15% tungsten copper argentum composite powder body of silver content is made；
5) the resulting composite granule of step 4) is centrifugated, is placed at 100 DEG C and is dried in vacuo to get finished product.
Embodiment 4:
A kind of preparation method of tungsten copper argentum composite powder body, includes the following steps:
1) it takes tungsten powder 1kg to be added in the wetting agent ethyl alcohol of 800ml to impregnate 1 hour, be rinsed after taking-up using deionized water；
2) then tungsten powder is added in the copper plating bath that volume is 40L, the content of each substance in copper plating bath are as follows: copper nitrate
10g/L, EDTA 25g/L are 12~14 using the pH that NaOH adjusts copper plating bath, and control temperature 60 C stirs 10 minutes, are then adopted
It is rinsed with deionized water, and copper facing tungsten powder is isolated using centrifuge；
3) it by glucose 100g, deionized water 10kg, is added in copper facing tungsten powder obtained above, and high speed machine stirs,
Copper facing tungsten powder is set to be uniformly dispersed；
4) under agitation, imidazoles 400g is added in the 1000ml aqueous solution of the 380g containing silver nitrate, complexing is made
Then complexing silver salt solution is added in the copper facing tungsten powder containing reducing agent, reacts 90 minutes, silver content is made by silver salt solution
20% tungsten copper argentum composite powder body；
5) the resulting composite granule of step 4) is centrifugated, is placed at 100 DEG C and is dried in vacuo to get finished product.
In order to verify the actual effect of tungsten copper argentum composite powder body obtained by preparation method provided by the invention, we are multiple to gained
It closes powder and has carried out every test, as can be seen that the partial size of the resulting tungsten copper argentum composite powder body of the method for the present invention from Fig. 1, Fig. 2
It is 5~50 μm, and gained composite granule has fine and close and uniform ground silver layer.
Electric conductivity test: electric conductivity is one of most important index of this product, and test basic device is used nonmetallic
Appropriate composite granule is added in cylindrical body, pressure used is 5kg/cm, measures resistance R with the digital micro-ohm table of DMR-5 type.
According to the calculation formula of resistivity: ρ=RS/L.
Wherein, R is the resistance of micro-ohm table measurement, unit Ω；S is the area of circle where cylindrical housings internal diameter, unit
For cm2；L is cylindrical housings inner cylinder height, unit cm.
Electromagnetic wave shielding: matrix uses aqueous polyurethane, and composite granule is conductive filler, and powder filled amount is 30% (matter
Amount ratio) conductive coating is prepared, film thickness is 25 microns.The survey formed using AV3618 vector network analyzer and rectangular waveguide
Test system, measurement frequency range are 2.6GHz~3.95GHz.
As a result as follows:
The electric conductivity comparison of composite granule obtained by 1 embodiment 1-4 of table
Since composite granule forms complete conductive network in conductive coating, there is good electromagnet shield effect, screen
Cover the reachable -108dB of peak value of efficiency.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of tungsten copper argentum composite powder body, which comprises the steps of:
1) tungsten powder is placed in wetting agent and is impregnated, rinsed after taking-up using deionized water；
2) the resulting tungsten powder of step 1) is placed in copper plating solution, is stirred, while controlled at 50~60 DEG C, reaction 10~
It is rinsed after 20min using deionized water, is centrifugated out copper facing tungsten powder, wherein the pH control of the copper plating solution is 11~14,
The copper plating solution is the mixed aqueous solution formed by soluble copper salt and copper ion complexing agent, and the mass ratio for controlling copper and tungsten is
0.10~0.15；
3) reducing agent solution is added in the resulting copper facing tungsten powder of step 2), stirring makes it be uniformly dispersed；
4) silver ion complexation agent is added in silver salt solution under stirring condition and complexing silver salt solution is made, after silver salt will to be complexed molten
Liquid is added in the resulting mixture of step 3), and 30~90min of reduction reaction occurs, and the tungsten that silver content is 5~15wt% is made
Cuprum argentum composite powder body, the silver ion complexation agent are trisodium citrate, triethanolamine, any one or more in imidazoles
Mixture；
5) the resulting tungsten copper argentum composite powder body of step 4) is washed, it is rear to be centrifugated；Vacuum drying to get.
2. preparation method according to claim 1, which is characterized in that silver salt and the silver ion complexation agent in step 4)
Mass ratio is 1:(1~5).
3. preparation method according to claim 1 or 2, which is characterized in that wetting agent described in step 1) is ethyl alcohol, different
The mixture of any one or more in propyl alcohol, acetone.
4. preparation method according to claim 3, which is characterized in that the mass ratio of tungsten powder and the wetting agent be (1~
10): 1.
5. preparation method according to claim 1 or 2, which is characterized in that copper ion complexing agent described in step 2) is
Any one in EDTA, trisodium citrate, the soluble copper salt refer to copper nitrate, copper sulphate, any one in copper chloride
Kind.
6. preparation method according to claim 5, which is characterized in that soluble copper salt described in step 2) and copper ion
The mass ratio of complexing agent is 1:(1~2.5).
7. preparation method according to claim 1 or 2, which is characterized in that reducing agent described in step 3) is formaldehyde, grape
Sugar, hydrazine sulfate, the mixture of any one or more in sodium potassium tartrate tetrahydrate.
8. preparation method according to claim 7, which is characterized in that the mass ratio of tungsten powder and the reducing agent be (1~
10): 1.
9. preparation method according to claim 1 or 2, which is characterized in that in step 5) vacuum drying temperature be 80~
100℃。
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