A kind of method silver-plated in glass microballoon copper coating and copper facing silver-plated glass beads
Technical field
The present invention relates to a kind of preparation method of electromagnetic shielding material is and in particular to one kind is plated on glass microballoon surface
The silver-plated method of copper, the invention still further relates to a kind of copper facing silver-plated glass beads obtained by this method.
Background technology
With the development of electronics industry, the various electric equipment conduct such as computer, messaging device, electronic communication equipment
The carrier of information technology is extensively applied in industry-by-industry, gives people class and brings great convenience, but electricity produced by equipment
Magnetic radiation, electromagnetic pollution have become as very important social problem.Due to conductive material, can to rely on high frequency band anti-
Radio magnetic wave reaches excellent shield effectiveness, is to prevent having of electromagnetic radiation pollution therefore using conductive rubber and electroconductive binder
Effect means.In terms of shielding electromagnetic interference, conductive rubber and electroconductive binder also can fill the gap of electronic equipment, instrument,
And the devices such as EMI shielding windows, ventilation waveguide can be connected.
At present, the species of conductive compound (binding agent) mainly has gold system, silver-colored system, copper system, the silver-plated system of copper, graphite system, stone
Black nickel plating system etc., considers electric conductivity, oxidative resistance and price factor, and silver system, the silver-plated system of copper are most widely used.With silver system
Conductive compound as conductive filler has the characteristics that good conductivity, oxidative resistance are good, but due to silver particles migration and price
Expensive the reason, limits its range.Using copper system as the conductive compound good conductivity of filler, but resistance to oxidation stability
Difference, easily oxidation ultimately becomes insulator to increase over time copper powder.In order to overcome these shortcomings, in prior art, such as
The preparation method of silver-plated copper powder is disclosed, the method is using silver-colored resistance to oxidation and stable spy in CN1049622A and CN1130553A
Point, remains the electric conductivity of copper, after copper powder defat, removes copper oxide-film with acid, is subsequently adding silver salt solution, makes copper replace silver
Ion, allows deposition of silver form layer protective layer, the good conductive copper powder of prepared oxidative resistance on Copper Powder Surface.With this copper silvering powder
The conductive rubber and binding agent good conductivity, oxidative resistance of preparation are good, price is more silver-colored is that powder is greatly lowered.But argentum powder, copper plate
Argentum powder have the shortcomings that one common be that density is big, in binding agent, these powder loadings are high, and the 75%-85% accounting for gross weight is left
The right side, leads to final electromagnetic shielding material conductive rubber and electroconductive binder density to increase, increased the use cost of material.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, one kind is provided to carry out copper facing on glass microballoon surface silver-plated
Method, by the method be obtained copper facing silver-plated glass beads, have the characteristics that density is little, silver content is low, conduct electricity very well.
For achieving the above object, the present invention employs the following technical solutions:
A kind of method silver-plated in glass microballoon copper coating, comprises the following steps:
1) it is roughened:Glass microballoon is placed in caustic, at 10~60 DEG C, filters after being slowly stirred 15~45 minutes,
And it is standby to neutrality with clean water;
2) it is sensitized:Glass microballoon after roughening treatment is placed in sensitizing solution, 5~30 points of sensitized treatment at 15~60 DEG C
Filter after clock, and with standby after clean water to neutrality;
3) reduce copper facing:Glass microballoon after sensitization is placed in copper plating solution, adds reducing solution under agitation, and
Reduction copper plating treatment filtered after 5~30 minutes at 30~70 DEG C, and with standby with water seal after clean water to neutrality;
4) replacement ag plating:Glass microballoon after copper facing is placed in silver plating solution, adds silver ammino solution under agitation,
And displacement silver plating reaction filtered after 5~40 minutes at 30~60 DEG C, and dried at 50~80 DEG C to neutral with clean water
Dry.
Preferably:Also removal step is included, described removal step is before described roughening step:Glass microballoon is placed in alkali
In liquid, stir process filtered after 10~50 minutes at 30~60 DEG C, and with clean water to neutral standby.
Preferably:Described alkali liquor is NaOH or KOH solution, and its concentration is 10~50wt%.
Preferably:Described caustic is hydrofluoric acid solution, and its concentration is 3~30wt%.
Preferably:Described sensitizing solution is the mixed liquor of stannous chloride solution and hydrochloric acid solution, wherein, stannous chloride solution
Concentration be 5~15g/L, the concentration of hydrochloric acid solution is 20ml~80ml/L.
Preferably:In terms of 1L, the consisting of of described copper plating solution:Copper sulfate:20~120g, EDTA and/or EDTA bis-
Sodium:40~150g, sodium potassium tartrate tetrahydrate and/Soluble tartar.:50~150g, ammonia:10~60, sodium hydroxide and/or potassium hydroxide:
1~10g, distilled water:Surplus.
Preferably:Described reducing solution is aldehydes or saccharide.
Preferably:Described aldehydes is 99% formalin, and by required copper facing gauge, its consumption is 50~120ml/L, institute
Stating saccharide is 50% glucose solution, and by required copper facing gauge, its consumption is 75~180ml/L.
Preferably:In terms of 1L, the consisting of of described silver plating solution:EDTA and/or EDETATE SODIUM:40~150g, winestone
Sour potassium sodium and/or Soluble tartar.:10~80g, sodium hydroxide and/or potassium hydroxide 1~10g/L, distilled water:Surplus.
A kind of copper facing silver-plated glass beads being obtained by said method, its inner core is 5~100 μm hollow or real for particle diameter
Heart glass microballoon, its surface is coated with copper coating and silvering outside interior successively.
The beneficial effects of the present invention is:1) the copper facing silver-plated glass beads that the method for the present invention is obtained, its surface are passed through
Silver-plated layer weight only account for the 5-15% of gross weight, make into silver-plated copper powder cost and be greatly lowered, being easy to industrial mass production makes
With;2) shown according to data document:The tap density of argentum powder is 10.4g/cm3, the tap density of copper powder is 8.7g/cm3, copper plating
The tap density > 8.7g/cm of argentum powder3, and copper facing silver-plated glass beads tap density provided by the present invention is < 8.7g/cm3,
The weight of product can be effectively reduced;3) copper facing silver-plated glass beads have the good electric conductivity of copper silvering powder, volume resistance
Rate≤10-3Ω cm, and the low specific surface area due to spherical glass beads, thus only need less silver can coat copper facing completely
Glass microballoon, and make prepared copper facing silver-plated glass beads have relatively low density, therefore reduce material cost and make
Use cost;4) there is storage stability good, it is adaptable to prepare conductive rubber, electrically-conducting paint and conduction the features such as heat-resist
The conductive materials such as binding agent.
Specific embodiment
With reference to specific embodiment, the specific embodiment of the present invention is described further.But the present invention simultaneously not only limits
In following embodiments.Unless otherwise noted, each raw material of the present invention all can be bought and can be obtained by market.
A kind of carry out the silver-plated method of copper facing on glass microballoon surface, preferably 5~100 μm of the particle diameter of described glass microballoon,
Comprise the following steps:
1) remove impurity:Glass microballoon is placed in alkali liquor, stir process filtered after 10~50 minutes at 30~60 DEG C, was used in combination
Clean water to neutral standby, to remove the impurity such as the greasy dirt on glass microballoon surface, wherein, described alkali liquor is concentration for 10~
The NaOH of 50wt% or KOH solution;
2) it is roughened:Roughening treatment is carried out with caustic to glass microballoon surface, described roughening treatment process is:Glass is micro-
Pearl is placed in caustic, at 10~60 DEG C, filters after being slowly stirred 15~45 minutes, and standby to neutrality with clean water;
Wherein, the preferred hydrofluoric acid solution of described caustic, its concentration is 3~30wt%;
3) it is sensitized:Glass microballoon after roughening treatment is placed in sensitizing solution, 5~30 points of sensitized treatment at 15~60 DEG C
Filter after clock, and with standby after clean water to neutrality;Wherein, described sensitizing solution is the mixed of stannous chloride solution and hydrochloric acid solution
Close liquid, wherein, stannous chloride (SnCl2·2H2O) concentration of solution is 5~15g/L, and the concentration of hydrochloric acid (HCl, 37%) solution is
20ml~80ml/L;
4) reduce copper facing:Glass microballoon after sensitization is placed in copper plating solution, adds reducing solution under agitation, and
Reduction copper plating treatment 5~30 minutes at 30~70 DEG C, copper plating solution is reacted with reducing solution, the copper of reduction is deposited on glass micro-
On pearl, form copper pre-plating layer;Then filter, and with clean water to neutrality after standby with water seal;Wherein, with 1g glass microballoon
Meter, the consumption of copper plating solution is 12.5~35.5ml, in every liter of copper plating solution, consisting of:Copper sulfate (CuSO4·5H2O):20
~120g, EDTA and/or EDETATE SODIUM:40~150g, sodium potassium tartrate tetrahydrate and/Soluble tartar.:50~150g, ammonia:10~60,
Sodium hydroxide and/or potassium hydroxide:1~10g, distilled water:Surplus;Described reducing solution is aldehydes or saccharide, wherein, described aldehydes
Preferably formaldehyde (99%) solution, by required copper facing gauge, its consumption is 50~120ml/L, the preferred glucose solution of described saccharide
(50%), by required copper facing gauge, its consumption is 75~180ml/l;The thickness of coating of copper can be by Cu in copper plating solution2+Content
Determine, when copper plating solution is for the 20%~120% of glass microballoon weight, in glass microballoon, the content of copper is 5%~40%;
5) replacement ag plating:Glass microballoon after copper facing is placed in silver plating solution, adds silver ammino solution under agitation,
And displacement silver plating reaction filtered after 5~40 minutes at 30~60 DEG C, and dried at 50~80 DEG C to neutral with clean water
Dry;Wherein, in terms of 1g starting glass microballon, the consumption of silver plating solution is:5g~15g;In every liter of silver plating solution, its composition
For:EDTA and/or EDETATE SODIUM:40~150g, sodium potassium tartrate tetrahydrate and/or Soluble tartar.:10~80g, sodium hydroxide and/or hydrogen
Potassium oxide 1~10g, distilled water:Surplus;The consisting of of described silver ammino solution:In every 200ml silver ammino solution, silver nitrate 7~24g,
Ammonia 50~170ml, distilled water:Surplus.
Embodiment 1
So that preparation copper facing amount 20wt%, silver-plated amount are for 5wt% glass microballoon as a example, its preparation method comprises the following steps:
1) remove impurity:The glass microballoon that 80g particle diameter is 30 μm is placed in the NaOH solution that 200ml concentration is 30wt%, in
Stir process 20 minutes at 40 DEG C, to remove the impurity such as the greasy dirt on glass microballoon surface, then filter and with clean water in
Standby after property;
2) it is roughened:Glass microballoon after remove impurity is processed is placed in the hydrofluoric acid solution that 100ml concentration is 20wt%, in 35
Filter after being stirred 15 minutes with the speed of 100rp at DEG C, and standby to neutrality with clean water;
3) it is sensitized:Glass microballoon after roughening treatment is placed in the sensitizing solution of 500ml, 20 points of sensitized treatment at 30 DEG C
Filter after clock, and with standby after clean water to neutrality;Wherein, described sensitizing solution is the stannous chloride of 10g/L and dense for concentration
Spend the mixed liquor of the hydrochloric acid solution for 60ml/L;
4) reduce copper facing:Glass microballoon after sensitization is placed in the copper plating solution of 1L, adds reduction under agitation
Liquid, and reduction copper plating treatment filtered after 20 minutes at 55 DEG C, and with standby with water seal after clean water to neutrality;Wherein,
In 1L copper plating solution, consisting of:Copper sulfate (CuSO4·5H2O):78g, EDETATE SODIUM:80g, sodium potassium tartrate tetrahydrate:76g, ammonia
Water:40ml, sodium hydroxide:4.5g, distilled water:Surplus;Described reducing solution is formaldehyde (99%) solution, by required copper facing gauge,
The consumption of described formaldehyde (99%) solution is 45ml/L;
5) replacement ag plating:Glass microballoon after copper facing is placed in 800ml silver plating solution, adds silver-colored ammonia under agitation
Solution, and displacement silver plating reaction filtered after 20 minutes at 30 DEG C, and with clean water to neutral drying at 65 DEG C
Copper facing silver-plated glass beads of the present invention;Wherein, the consisting of of every liter of silver plating solution:EDETATE SODIUM:100g, Soluble tartar.
Sodium:50g, sodium hydroxide 5g, distilled water:Surplus;The consisting of of described silver ammino solution:In every 200ml silver ammino solution, silver nitrate is
7.8g, ammonia is 12ml, distilled water:Surplus.
Embodiment 2
Taking prepare the glass microballoon of the silver-plated 8wt% of copper facing amount 40wt% as a example, described preparation method comprises the following steps:
1) remove impurity:The glass microballoon that 60g particle diameter is 30 μm is placed in the NaOH solution that 200ml concentration is 30wt%, in
Stir process 20 minutes at 40 DEG C, to remove the impurity such as the greasy dirt on glass microballoon surface, then filter and with clean water in
Standby after property;
2) it is roughened:Glass microballoon after remove impurity is processed is placed in the hydrofluoric acid solution that 100ml concentration is 20wt%, in 35
Filter after being stirred 15 minutes with the speed of 100rp at DEG C, and standby to neutrality with clean water;
3) it is sensitized:Glass microballoon after roughening treatment is placed in the sensitizing solution of 500ml, 20 points of sensitized treatment at 30 DEG C
Filter after clock, and with standby after clean water to neutrality;Wherein, described sensitizing solution is the stannous chloride of 10g/L and dense for concentration
Spend the mixed liquor of the hydrochloric acid solution for 60ml/L;
4) reduce copper facing:Glass microballoon after sensitization is placed in the copper plating solution of 2L, adds reduction under agitation
Liquid, and reduction copper plating treatment filtered after 20 minutes at 55 DEG C, and with standby with water seal after clean water to neutrality;Wherein,
The consisting of of every liter of copper plating solution:Copper sulfate (CuSO4·5H2O):78g, EDETATE SODIUM:80g, sodium potassium tartrate tetrahydrate:76g, ammonia:
40ml, sodium hydroxide:4.5g, distilled water:Surplus;By required copper facing gauge, the consumption of described formaldehyde (99%) solution is
100ml/L;
5) replacement ag plating:Glass microballoon after copper facing is placed in 800ml silver plating solution, adds silver-colored ammonia under agitation
Solution, and displacement silver plating reaction filtered after 30 minutes at 30 DEG C, and with clean water to neutral drying at 60 DEG C
Copper facing silver-plated glass beads of the present invention;Wherein, the consisting of of every liter of silver plating solution:EDETATE SODIUM:110g;Soluble tartar.
Sodium:60g, sodium hydroxide 6g, distilled water:Surplus;Described silver ammino solution, consisting of:In every 200ml silver ammino solution, silver nitrate
For 12.4g, ammonia is 20ml, distilled water:Surplus.
The glass microballoon that embodiment 1 and 2 is obtained enters line density and conducting performance test, and its test result is as shown in table 1,
Wherein, the method for testing of resistance is:YST587.6-2006;The method of testing of tap density is GB/T5162-2006.
Table 1 glass microballoon the performance test results
|
Copper content (%) |
Silver content (%) |
Powder resistance (m Ω cm) |
Tap density (g/cm3) |
Embodiment 1 |
20 |
5 |
0.9 |
1.38 |
Embodiment 2 |
40 |
8 |
0.7 |
1.51 |
As can be seen from Table 1, using the glass microballoon obtained by the present invention, the silver-plated layer weight on its surface accounts for the hundred of gross weight
Divide than low so that silver-plated copper powder cost is greatly lowered, be easy to industrial mass production and use.And, prepared is double-deck
Copper facing silver-plated glass beads, its specific insulation≤10-3Ω cm, has that coating is uniform, density is little, electric conductivity and storage characteristics are good
Feature, the thickness of preplating layers of copper determines the final conductive layer of glass microballoon, when copper plate is relatively thin, its electric conductivity
Slightly better than silver-plated glass beads, when thickness of coated copper layer is thicker, its electric conductivity is equivalent to copper facing silver glass microballoon.It is applied to system
The compounds such as standby conductive rubber, wire coating and electroconductive binder.
Specific embodiment described in the invention is served only for implementing process to copper facing silver-plated glass beads preparation method
Detailed description, rather than for concrete restriction to its preparation method.Any modification that the method is carried out and improvement, special
In sharp scope or category, the replacement of similar or close material and use, belong to scope of patent protection of the present invention.