CN107617739A - 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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- CN107617739A CN107617739A CN201710833319.6A CN201710833319A CN107617739A CN 107617739 A CN107617739 A CN 107617739A CN 201710833319 A CN201710833319 A CN 201710833319A CN 107617739 A CN107617739 A CN 107617739A
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Abstract
The present invention relates to a kind of preparation method of tungsten copper argentum composite powder body,Soaked including tungsten powder is placed in wetting agent,Tungsten powder is placed in copper facing in the copper plating solution of alkalescence afterwards,It is the alkaline complex copper ion solution formed by soluble copper salt and copper ion complexing agent in copper plating solution,Reductant 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 generation reduction reaction,Tungsten copper argentum composite powder body is made,Tungsten copper argentum composite powder body obtained by the inventive method has that copper facing is silver-plated smooth and uniformity is good,Coating is tightly combined,The features such as purity is high,And it can be mass produced,It can be widely applied to middle/high-voltage electrical appliance,Communication,Aviation,Machinery,Electronics,It is metallurgical,The field such as 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 side of tungsten copper argentum composite powder body
Method, belong to chemical surface treatment technical field.
Background technology
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 coefficient of expansion is small, particularly tungsten
Copper silver composite material has outstanding arc resistant ablation, resistance fusion welding and good conduction, thermal conductivity, is widely used in mesohigh
The fields such as electrical equipment, communication, aviation, machinery, electronics, metallurgy, space flight and military project.Tungsten copper silver composite material is because possessing 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, exist again as weldering electrode material
Space industry is applied.Electronic Encapsulating Technology is the important component of modern electronics industry, encapsulation process chips and base
Interconnection technique level between plate, chip and circuit limits electronic product and developed to miniaturization, portability.In recent years, electronics
The projection of industry integrated circuit is that the tungsten copper silver composite material for possessing excellent encapsulation performance brings the opportunity to develop of a new round.
Tungsten copper argentum composite powder body has uniform small grains, electric-conductivity heat-conductivity high, specific surface area, and wetability is good greatly, between metal
Many advantages, such as, it is extremely advantageous to follow-up shaping and sintering circuit in field of metallurgy.In recent years for ultra-fine uniformly tungsten copper silver
Composite granule produces research intimately.It is current prepare tungsten copper argentum composite powder body method it is numerous, mainly including mechanical alloying method,
Sol-gel method, spray drying process, electroless plating method etc..
Machine-alloying has that technique is flexibly simple, and without hot environment, energy consumption is low, and yield is big, and the composite powder worn into is equal
It is even and fine small, but repeatedly grinding can increase the iron content in composite powder for a long time, and this can influence the conductive hot property of composite granule.
Sol-gel method has that reaction temperature is low, and reaction controllability is high, and advantage, the powders prepared such as out-phase side reaction is few have pure
Degree is high, and chemical uniformity is good, and structure is single tiny, the advantages such as heat treatment temperature is low.But there is long preparation period, cost in the technique
Height, the problems such as volume production difficulty.Spray drying process each operation is easily controllable, and the oxide precursor after dry nebulization is typically in ball
Shape ghost shape, product impurity is low, is adapted to large-scale industrial production, but process is more, high energy consumption.
The content of the invention
The present invention is for the existing machine-alloying for preparing tungsten copper argentum composite powder body, sol-gel process, spray drying process
A kind of existing deficiency, there is provided preparation method of tungsten copper argentum composite powder body.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of tungsten copper argentum composite powder body, comprises the following steps：
1) tungsten powder is placed in wetting agent and soaked, deionized water rinsing is used after taking-up；
2) tungsten powder obtained by step 1) is placed in copper plating solution, stirred, while it is 50~60 DEG C to control temperature, reaction 10
Deionized water rinsing is used after~20min, centrifuges 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 that is made up of soluble copper salt, copper ion complexing agent is formed, control copper and
The mass ratio of tungsten is 0.10~0.15；
3) reductant solution is added in the copper facing tungsten powder obtained by 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 mixture obtained by 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) silver-plated copper powder obtained by step 4) is washed, it is rear to centrifuge；Vacuum drying, is produced.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, the silver ion complexation agent described in step 4) is any one in trisodium citrate, triethanolamine, 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 any one in silver nitrate, silver acetate.
Further, the wetting agent described in step 1) is the mixing of any one or more in ethanol, isopropanol, acetone
Thing, the mass ratio of tungsten powder and the wetting agent is (1~10)：1.
Further, the copper ion complexing agent described in step 2) be EDTA, any one in trisodium citrate, it is described can
Dissolubility mantoquita refers to any one in copper nitrate, copper sulphate, copper chloride.
Further, the mass ratio of the 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 any one in formaldehyde, glucose, hydrazine sulfate, sodium potassium tartrate tetrahydrate
Or a variety of mixtures, the mass ratio of tungsten powder and the reducing agent is (1~10)：1.
Further, vacuum drying temperature is 80~100 DEG C in step 5).
The beneficial effects of the invention are as follows：
1) method provided by the invention uses electronation technology, and the pre-treating technology of tungsten powder is using wetting agent immersion technology
Instead of traditional roughening, sensitization, activating technology, using new complexing agent prescription, in the reduction process of silver ion, in copper powder
Surface forms galactic nucleus and grown up, and forms the smooth silver layer of continuous dense uniform, cost is low, it is easy to accomplish large-scale production；
2) the tungsten copper argentum composite powder body obtained by the inventive method have copper facing is silver-plated smooth and uniformity is good, coating combine it is tight
Close, the features such as purity is high, and can be mass produced, it can be widely applied to middle/high-voltage electrical appliance, communication, aviation, machinery, electricity
The fields such as son, metallurgical, space flight and military project.
Brief description of the drawings
Fig. 1 is 400 times of magnified sweep electromicroscopic photographs of the gained tungsten copper argentum composite powder body of the embodiment of the present invention 1；
Fig. 2 is 5000 times of magnified sweep electromicroscopic photographs of the gained tungsten copper argentum composite powder body of the embodiment of the present invention 1；
Embodiment
The principle and feature 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 present invention.
Embodiment 1：
A kind of preparation method of tungsten copper argentum composite powder body, comprises the following steps：
1) take tungsten powder 1kg to be added in 250ml wetting agent ethanol to soak 1 hour, deionized water rinsing is used after taking-up；
2) and then by tungsten powder it is added in the copper plating bath that volume is 40L, the content of each material is in copper plating bath：Copper nitrate
10g/L, EDTA 25g/L, using NaOH adjust copper plating bath pH be 11~12, control temperature for 60 DEG C stirring 10 minutes, then
Copper facing tungsten powder is isolated using deionized water rinsing, and using centrifuge；
3) by formalin 120mL, deionized water 10kg, add in copper facing tungsten powder obtained above, and high speed machine stirs
Mix, copper facing tungsten powder is uniformly dispersed；
4) under agitation, trisodium citrate 220g is added in the 1000ml aqueous solution of the 80g containing silver nitrate, made
Into complexing silver salt solution, silver salt solution then will be complexed, will be added in the copper facing tungsten powder containing reducing agent, and reacted 30 minutes, be made
The tungsten copper argentum composite powder body of silver content 5%；
5) composite granule obtained by step 4) is centrifuged, is placed at 80 DEG C and is dried in vacuo, get product.
Embodiment 2：
A kind of preparation method of tungsten copper argentum composite powder body, comprises the following steps：
1) take tungsten powder 1kg to be added in 130ml wetting agent isopropanol to soak 1 hour, rushed after taking-up using deionized water
Wash；
2) and then by tungsten powder it is added in the copper plating bath that volume is 40L, the content of each material is in copper plating bath：Copper chloride
10g/L, EDTA 10g/L, using NaOH adjust copper plating bath pH be 11~12, control temperature for 50 DEG C stirring 15 minutes, then
Copper facing tungsten powder is isolated using deionized water rinsing, and using centrifuge；
3) by sodium potassium tartrate tetrahydrate 120g, deionized water 10kg, add in copper facing tungsten powder obtained above, and high speed machine stirs
Mix, copper facing tungsten powder is 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) composite granule obtained by step 4) is centrifuged, is placed at 80 DEG C and is dried in vacuo, get product.
Embodiment 3：
A kind of preparation method of tungsten copper argentum composite powder body, comprises the following steps：
1) take tungsten powder 1kg to be added in 1250ml wetting agent acetone to soak 1 hour, rushed after taking-up using deionized water
Wash；
2) and then by tungsten powder it is added in the copper plating bath that volume is 40L, the content of each material is in copper plating bath：Copper sulphate
10g/L, trisodium citrate 15g/L, the pH that copper plating bath is adjusted using NaOH is 12~14, and control temperature 60 C stirs 20 minutes,
Then deionized water rinsing is used, and copper facing tungsten powder is isolated using centrifuge；
3) by hydrazine sulfate 200g, deionized water 10Kg, add 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 the 1000ml aqueous solution, complexing silver salt solution is made, then will be complexed silver salt solution, is added to the copper facing tungsten powder containing reducing agent
In, react 90 minutes, the tungsten copper argentum composite powder body of silver content 15% is made；
5) composite granule obtained by step 4) is centrifuged, is placed at 100 DEG C and is dried in vacuo, get product.
Embodiment 4：
A kind of preparation method of tungsten copper argentum composite powder body, comprises the following steps：
1) take tungsten powder 1kg to be added in 800ml wetting agent ethanol to soak 1 hour, deionized water rinsing is used after taking-up；
2) and then by tungsten powder it is added in the copper plating bath that volume is 40L, the content of each material is in copper plating bath：Copper nitrate
10g/L, EDTA 25g/L, the pH that copper plating bath is adjusted using NaOH is 12~14, and control temperature 60 C stirs 10 minutes, then adopts
Copper facing tungsten powder is isolated with deionized water rinsing, and using centrifuge；
3) by glucose 100g, deionized water 10kg, add 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
Silver salt solution, then complexing silver salt solution is added in the copper facing tungsten powder containing reducing agent, reacts 90 minutes, silver content is made
20% tungsten copper argentum composite powder body；
5) composite granule obtained by step 4) is centrifuged, is placed at 100 DEG C and is dried in vacuo, get 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 answered gained
Close powder and carried out every test, as can be seen that the particle diameter of the tungsten copper argentum composite powder body obtained by the inventive method from Fig. 1, Fig. 2
For 5~50 μm, and gained composite granule has fine and close and uniform ground silver layer.
Electric conductivity is tested：Electric conductivity is one of most important index of this product, and it is tested basic device and used nonmetallic
Appropriate composite granule is added in cylinder, pressure used is 5kg/cm, and resistance R is determined with the digital micro-ohm table of DMR-5 types.
According to the calculation formula of resistivity：ρ=RS/L.
Wherein, the resistance that R determines for micro-ohm table, unit Ω；The area of S circles where cylindrical housings internal diameter, unit
For cm2；L be 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) electrically-conducting paint is prepared, film thickness is 25 microns.The survey formed using AV3618 vector network analyzers and rectangular waveguide
Test system, measurement frequency range are 2.6GHz~3.95GHz.
As a result it is as follows：
The electric conductivity contrast of composite granule obtained by the embodiment 1-4 of table 1
Because composite granule forms complete conductive network in electrically-conducting paint, there is good electromagnet shield effect, shield
Cover the reachable -108dB of peak value of efficiency.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of tungsten copper argentum composite powder body, it is characterised in that comprise the following steps：
1) tungsten powder is placed in wetting agent and soaked, deionized water rinsing is used after taking-up；
2) tungsten powder obtained by step 1) is placed in copper plating solution, stirred, while it is 50~60 DEG C to control temperature, reaction 10~
Deionized water rinsing is used after 20min, centrifuges out copper facing tungsten powder, wherein, the pH controls of the copper plating solution are 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) reductant solution is added in the copper facing tungsten powder obtained by 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 will to be complexed silver salt molten
Liquid is added in the mixture obtained by 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；
5) silver-plated copper powder obtained by step 4) is washed, it is rear to centrifuge；Vacuum drying, is produced.
2. preparation method according to claim 1, it is characterised in that the silver ion complexation agent described in step 4) is lemon
The mixture of any one or more in sour trisodium, triethanolamine, imidazoles.
3. preparation method according to claim 1 or 2, it is characterised in that silver salt and the quality of the silver ion complexation agent
The ratio between be 1：(1~5).
4. preparation method according to claim 1 or 2, it is characterised in that wetting agent described in step 1) is ethanol, different
The mixture of any one or more in propyl alcohol, acetone.
5. preparation method according to claim 4, it is characterised in that the mass ratio of tungsten powder and the wetting agent for (1~
10)：1.
6. preparation method according to claim 1 or 2, it is characterised in that the copper ion complexing agent described in step 2) is
Any one in EDTA, trisodium citrate, the soluble copper salt refers to any one in copper nitrate, copper sulphate, copper chloride
Kind.
7. preparation method according to claim 6, it is characterised in that soluble copper salt and copper ion described in step 2)
The mass ratio of complexing agent is 1：(1~2.5).
8. preparation method according to claim 1 or 2, it is characterised in that reducing agent described in step 3) is formaldehyde, grape
The mixture of any one or more in sugar, hydrazine sulfate, sodium potassium tartrate tetrahydrate.
9. preparation method according to claim 8, it is characterised in that the mass ratio of tungsten powder and the reducing agent for (1~
10)：1.
10. preparation method according to claim 1 or 2, it is characterised in that in step 5) vacuum drying temperature be 80~
100℃。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111390195A (en) * | 2020-03-27 | 2020-07-10 | 陕西理工大学 | Micro-interface quantum-scattering-free tungsten-copper alloy and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1674176A1 (en) * | 2003-10-15 | 2006-06-28 | Sumitomo Electric Industries, Ltd. | Granular metal powder |
| CN102009173A (en) * | 2010-12-27 | 2011-04-13 | 北京科技大学 | Method for preparing copper-clad tungsten tungsten-copper composite powder |
| CN102814496A (en) * | 2012-08-14 | 2012-12-12 | 烟台德邦科技有限公司 | Silver-plated copper powder and preparation method thereof |
| CN103464742A (en) * | 2013-09-18 | 2013-12-25 | 武汉理工大学 | Preparation method of copper-cladded silver-clad tungsten composite clad powder |
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2017
- 2017-09-15 CN CN201710833319.6A patent/CN107617739B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1674176A1 (en) * | 2003-10-15 | 2006-06-28 | Sumitomo Electric Industries, Ltd. | Granular metal powder |
| CN102009173A (en) * | 2010-12-27 | 2011-04-13 | 北京科技大学 | Method for preparing copper-clad tungsten tungsten-copper composite powder |
| CN102814496A (en) * | 2012-08-14 | 2012-12-12 | 烟台德邦科技有限公司 | Silver-plated copper powder and preparation method thereof |
| CN103464742A (en) * | 2013-09-18 | 2013-12-25 | 武汉理工大学 | Preparation method of copper-cladded silver-clad tungsten composite clad powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111390195A (en) * | 2020-03-27 | 2020-07-10 | 陕西理工大学 | Micro-interface quantum-scattering-free tungsten-copper alloy and preparation method and application thereof |
| CN111390195B (en) * | 2020-03-27 | 2022-05-24 | 陕西理工大学 | Micro-interface quantum scattering-free tungsten-copper alloy and preparation method and application thereof |
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