CN103060780B - Preparation method of nickel-coated copper powder for conductive rubber - Google Patents
Preparation method of nickel-coated copper powder for conductive rubber Download PDFInfo
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Abstract
The invention provides a preparation method of a nickel-coated copper powder for a conductive rubber, and belongs to the technical field of surface treatment of powder bodies. According to the preparation method, a chemical reduction method is carried out, a plating solution and a pH (Potential Of Hydrogen) regulator are reasonably prepared at a room-temperature condition, therefore the surface of copper powder is subjected to basic deoxidation in order to realize the purpose of optimizing a plating-coating process; the method of continuously dropping the mixed solution of ammonia water and sodium hydroxide is carried out, thereby the stability of the plating solution is maintained, and the pH value of the plating solution is maintained to between 11 to 14; and the prescriptions under different concentrations are prepared, therefore the nickel-coated copper powder containing different nickel contents can be obtained. The nickel-coated copper powder prepared by the preparation method provided by the invention is complete, continuous and dense; the plating solution is clear; the nickel ions are completely transformed; the plating layer has the thickness up to more than 1 micron; the magnetizing strength of the power bodies is more than 10emu/g; the nickel-coated copper powder contains 30wt.% of nickel; and the shielding effectiveness of the conductive rubber at middle-high frequency can be more than 50 by testing through a coaxial method when the mass is filled to 220 parts.
Description
Technical field
The invention belongs to powder surface processing technology field, relate to the method for the coated nickel of a kind of Copper Powder Surface, the nickel coated copper powder of preparation has the features such as technique is simple, coated completely, magnetic is good, is desirable electromagnetic shielding conductive loading material of rubber.
Background technology
Along with the development of present electronic technology, the electronic apparatus of various digitizings, high frequency brings a lot of a large amount of electromagnetic pollutions that also brought easily to our life simultaneously.Therefore, the research of electromagnetic shielding material is had to very important realistic meaning.
Electromagnetic shield rubber is a kind of very important electromagnetic shielding material, and it is mainly comprised of rubber and conductive filler material.Conventional conductive rubber filler has silver-coated copper powder, silver coated aluminum powder, nickel coated copper powder, nickel coated graphite powder etc.Fine silver has fabulous electroconductibility and oxidation-resistance, but under wet heat condition and conductive media condition, easily ELECTROMIGRATION PHENOMENON occurs and cause short circuit, and fine silver is expensive, free settling in rubber matrix; The electroconductibility of copper is only second to silver, cheap, but oxidation-resistance is poor, and the copper powder electroconductibility after oxidation sharply declines, and has lost the advantage as conductive filler material; Nickel powder has good oxidation-resistance and ferromegnetism, be usually used in coating and plastics and do the fields such as conducting pigment shielding electromagnetic interference and radio frequency interference, but the electroconductibility of nickel powder is poor.Nickel coated copper powder is that nickel layer has improved oxidation-resistance and the electroconductibility of copper powder, increases the ferromegnetism of powder simultaneously, applicable to large-area shielding material, is desirable conductive rubber filler, has wide market and researching value at the coated one deck nickel of Copper Powder Surface.
Tradition nickel plating technology is ripe, and Using Sodium Hypophosphite is reductive agent, and nickel is deposited on substrate surface with Ni-P alloy form, but electroless nickel plating on inorganic powder just became attention rate focus in recent years.At present, nickel coated copper powder mainly passes through chemical preparation.Chemical reduction method is in solution, to add reductive agent, by reductive agent, provides electronics that the metallics in solution is reduced, and is deposited on and on body material, forms metal plating.Generally, chemical reduction method requires deposited base material to have autocatalysis activity, adopts pre-treatment sensitization, activating process to improve powder surface activity.Branch copper powder has powerful specific surface area, and surfactivity is high, has certain autocatalysis ability, but also oxidizable, electroconductibility decline of powder.
April 4 2005 patent US20060222554A1(applying date, open day on October 5th, 2006) or December 13 2005 CN101124059A(applying date, open day on February 13rd, 2008) provide a kind of preparation method of nickel-copper powder of diffusion-bonded.This invention selects the powder of metallic nickel and copper or the two oxide compound or sheet to carry out 100～1100 ℃ of diffusion-bonded 1～120 minute or 400～700 ℃ of diffusion-bonded 20～60 minutes, obtains to expand to be suitable for adding the mixture in sintered steel and alloy.The method adopts high-temperature heat treatment to prepare nickel-copper precursors mixture of diffusion-bonded, and powder provides nickel, copper, mixing ambrose alloy, lower to the oxidation-resistance requirement of powder, is mainly used in sintered steel and steel alloy.
At on 07 15th, the 2005 patent WO2006009097(applying date, open day on 01 26th, 2006) or on 07 15th, the 2005 CN1988973A(applying date, open day on 06 27th, 2007) or on 07 15th, 2005 CA2574173(applying date, open day on 01 26th, 2006) manufacture method of a kind of conductive paste of the wiring part that can form the electroconductibility that electronic circuit uses with the nickel-plated copper powder of scale resistance be provided.This invention is with palladium chloride solution activated copper powder surface, and adopting hydrazine (hydrazine) is reductive agent, the nickel-plated copper powder that the nickel massfraction that can obtain 0.5～10 micron at 30～70 ℃ is 0.1%～10%.This invention nickel-plated copper powder and manufacture method, can be applicable to by the wiring part wire-conducting performance cream conductive material with the manufacture such as sintering or resin multi-layer substrate simultaneously of the low temperature such as ceramic substrate.It is reductive agent that hydrazine (hydrazine) is take in this invention, and hydrazine has stronger toxicity, and environment is had to certain pollution, and equipment solidity to corrosion is also had to higher requirement; With 5% palladium chloride solution, carry out activation treatment, then washing is processed, and has increased pretreatment procedure, has reduced powder preparation efficiency, waste water resource.
On December 27 2006 patent CN101209493A(applying date, open day is on July 2nd, 2008) preparation method of nano core-shell type copper-nickel bimetal powder body is provided.This invention is in a kind of technology of preparing of nanometer spherical copper powder; in the single nickel salt mixing solutions that macromolecule dispersant and the thiocarbamide of take are coordination agent; at 75～90 ℃ of plating temperatures; make nickel ion and copper generation replacement(metathesis)reaction; at the partly or entirely coated nickel in the surface of copper ultramicron, form a kind of core-shell type copper-nickel bimetal nano-powder.Nano core-shell type copper-nickel bimetal powder body prepared by the method is mainly as making additive in lubricating oil and lubricating grease extreme-pressure anti-friction additive, powder metallurgy, or falls the raw material of material, self-lubricating material, antifriction material, diamond tool and electrical carbon product or do the application of additive as porous material, anti-biotic material, antifouling paint, electro-conductive material, magnetic.This inventive method, nickel simple substance is limited at the plating of Copper Powder Surface, can not reach completely coated; Adopt macromolecule dispersant, increase recipe ingredient, increase formula complicacy; The non-normal temperature of plating temperature, has increased plating cost.
On March 17 2006 patent CN1817521A(applying date, open day is on August 16th, 2006) composite metal powder of the coated nickel of Copper Powder Surface that a kind of Wet-process metallurgy method prepares powder used in metallurgy is provided.This invention is at 80～90 ℃ of temperature, the 2mol/L NaOH solution of take is pH adjusting agent, pH=11.5～13.5 time, preparation 35～45g/L nickel sulfate solution, every liter of nickel sulfate solution slowly add the plating solution of 75～95ml hydrazine, obtain the nickel coated copper powder that nickel content is 17%～25%.The prepared cladding powder of the method has the characteristic that mechanically mixing powder does not have, and as being easy to alloying in powder metallurgy, segregation does not occur in use procedure.The method be take hydrazine as reductive agent, has stronger toxicity, and etching glass, rubber, leather, cork etc., have relatively high expectations to the stopping property of equipment, solidity to corrosion; Plating process is carried out under non-normal temperature condition, has increased energy input.
On 01 19th, the 2010 patent CN101733401A(applying date, open day on 06 16th, 2010) a kind of preparation method of nickel-plated copper powder is provided.The method activates 20～80min, is washed to after neutrality with 15%～75% hydrochloric acid soln, then with 5～10% hydrochloric acid soln pickling 5～15min, washing 3～5 times to neutral, and then in nickel-plating liquid, carry out electroless plating and obtain nickel-plated copper powder.The method makes in conductive resin that product is mainly used in conduction demand, electrically conducting coating, electric conduction paint, conductive plastics, conductive rubber.This invention preparation method, pretreatment process is complicated, has increased repeatedly and has cleaned, waste water resource; In preparation process, plating solution needs heating (alkaline plating temperature is 35-50 ℃, and acid plating temperature is 80～90 ℃), and temperature control requirement is higher, and acid formula plating temperature is higher, and energy input is higher.
Mainly there is following difficult point in the research of in sum, carrying out at present copper powder nickel plating:
(1) copper powder complex process: the pre-treatments such as activation, sensitization, pickling not only increase plating process, and after processing, be accompanied by repeatedly washing, more increased water resource waste; (2) additional energy source input: the heating of plating process, not only increased energy consumption, plating technic is controlled and had relatively high expectations; (3) there is environmental pollution: take hydrazine as reductive agent and repeatedly clean, environment is had to larger pollution; (4) cost is higher: adopt Palladous chloride activation, cost is higher.
Summary of the invention
The present invention is directed to the problem that prior art exists, a kind of method that technique is simple, coated room temperature is completely prepared nickel coated copper powder is provided.The prepared nickel coated copper powder of the present invention is as conductive filler material, for the conductive rubber of electromagnetic shielding material.
The preparation method of a kind of nickel coated copper powder provided by the present invention, it is characterized in that by reasonable preparation plating solution and pH adjusting agent, the stable pH value of controlling, make copper powder pre-treatment and plating process integrated, stablize plating process, reach the object of simplification technique, room temperature plating.Preparation process comprises the following steps:
(1) pH value conditioning agent preparation: take two parts of sodium hydroxide a
1, a
2, be configured to respectively solution A
1, A
2; Measure two parts of strong aqua B
1, B
2; By B
2slowly add A
2, add appropriate amount of deionized water, stir, be designated as solution C;
(2) plating solution preparation: take single nickel salt, Trisodium Citrate, sodium hypophosphite, add in deionized water and dissolve, do not stop to stir, each component is fully dissolved, obtain plating solution;
(3) plating process: under stirring at room condition, by the A in step (1)
1solution slowly adds in the plating solution of step (2); Take copper powder, gradually copper powder is joined in plating solution, copper powder is uniformly dispersed; Add gradually subsequently B
1, do not stop to stir; In plating process, solution C is continuously added drop-wise in system, bath pH value is tended towards stability; In the plating later stage, plating solution clarification, powder gray, continue to stir for some time, until powder is uniformly dispersed, nothing is reunited, stops stirring;
(4) post-processed: powder is sedimentation completely in plating solution, removes plating solution, obtains nickel coated copper powder; Adopt clear water to clean powder to neutral, then use soaked in absolute ethyl alcohol; Last vacuum-drying obtains nickel-plated copper powder.
Above-mentioned steps (1) sodium hydroxide: a
2=(0.5～1) a
1; Strong aqua is (25～28) wt.%, B
2=(0.2～0.5) B
1;
Above-mentioned steps (1) solution A
1, A
2with complete dissolved hydrogen sodium oxide, be advisable, liquor capacity: A
2< C;
A in above-mentioned steps (1) solution C
2concentration be 100～300g/L, B
2consumption be 80～100ml/L;
Above-mentioned steps (3) sodium hydroxide a
1concentration in plating solution is 10g～40g/L; 20g/L is best;
Above-mentioned steps (3) B
1consumption in plating solution is 10～150ml/L, and 80～100ml/L is best;
In above-mentioned steps (3): the mol ratio of single nickel salt, sodium hypophosphite, Trisodium Citrate is 1: (1～3): (0.5～1);
Above-mentioned steps (3) copper powder consumption is that 20～33.3g/L, concentration of nickel sulfate are that 23～100g/L, sodium hypophosphite concentration are that 28～100g/L, sodium citrate concentration are 26～110g/L;
If preferably above-mentioned steps makes nickel content 30wt.% in the finished product, the optimum formula of step (3) in advance: the total mass≤200g of copper powder, copper powder 20g/L, single nickel salt 39g/L, sodium hypophosphite 40g/L, Trisodium Citrate 44g/L in plating solution; If copper powder total mass >200g, copper powder 33.3g/L, single nickel salt 65g/L, sodium hypophosphite 60g/L, Trisodium Citrate 100g/L in plating solution;
If above-mentioned steps makes nickel content 40wt.% in the finished product, the optimum formula optimum formula of step (3) in advance: the total mass≤200g of copper powder, copper powder 20g/L, single nickel salt 60g/L, sodium hypophosphite 55g/L, Trisodium Citrate 68g/L in plating solution; The total mass >200g of copper powder, copper powder 33.3g/L, single nickel salt 100g/L, sodium hypophosphite 80g/L, Trisodium Citrate 100g/L in plating solution;
In above-mentioned steps (3), copper powder particle size is 45～75 μ m, and pattern is dendroid or spherical;
Above-mentioned steps (3) drips solution C, also can change into and drip continuously separately A simultaneously
2with B
2;
Above-mentioned steps (3) solution C drips 20～60min continuously, and drop rate is (1～12) ml/min, plating solution pH=(11～14); Best pH=(12～13);
Above-mentioned steps (3) the plating reaction times is 20～60min; After plating solution clarification, continue to stir for (10～60) min, until powder disperses to obtain grey slurry;
Above-mentioned steps (4) is cleaned, is protected by dehydrated alcohol or acetone and other organic solvent, soaks (5～10) min;
Above-mentioned steps (4) vacuum-drying temperature is (80～100) ℃, and the time is (10～12) h;
The present invention carries out the surface modifying method of electroless plating one deck nickel to copper powder.Copper powder is oxidizable, greatly reduces the conductivity of powder; Nickel layer can effectively improve the oxidation-resistance of powder.But existing powder nickel plating technology is complicated, plating temperature is higher, has increased equipment requirements and plating cost.This patent is by reasonable preparation conditioning agent and control pH, makes copper powder pre-treatment and plating process integrated, realizes room temperature plating.
In plating solution layoutprocedure, single nickel salt is water-soluble, has hydrolysis tendency, forms six hydration nickel ions, is acid after hydrolysis:
Ni(H
2O)
6 2+→[Ni(H
2O)
5OH]
++H
+→Ni(H
2O)
4(OH)
2+2H
+
When adding sodium hypophosphite, due to nickelous hypophosphite [Ni (H
2pO
2) 6H
2o] solubleness [37.65g/ (100gH
2o)] larger, so plating solution can not decompose.When bath pH value raises, the water molecules in hydration nickel ion is by OH
-replace, the whole chelatings of nickel ion, exist with maximum stable state.
When solution slowly adds ammoniacal liquor, make the oxide compound of copper that complex reaction occur in basic solution, finally with [Cu (NH
3)
2]
2+or [Cu (NH
3)
2]
+be present in plating solution, reach the object of removing oxide film.The chemical reaction occurring mainly contains:
Cu
2O+2OH
-+4[NH
4]
+=2[Cu(NH
3)
2]
++3H
2O
CuO+2OH
-+4[NH
4]
+=[Cu(NH
3)
4]
2++3H
2O
Cu(OH)
2+2OH
-+4[NH
4]
+=[Cu(NH
3)
4]
2++4H
2O
Meanwhile, because plating solution is in whipped state, in plating solution, can dissolve a certain amount of O
2.Under the catalysis of ammonium radical ion, Copper Powder Surface can react:
Cu+0.5O
2+2OH
-+4[NH
4]
+=[Cu(NH
3)
4]
2++3H
2O
Therefore, adopt the lower ammonia radical ion deoxidation of alkalescence to process significant to the Copper Powder Surface plating of complex topography.In conjunction with alkaline nickel plating technology, the Copper Powder Surface that plating solution infiltrates just can form fine and close overlay coating in active state, reaches completely coated, further Optimization Technology.
According to the hydride transmission theory of P.Hersch, H
2pO
2 -in alkaline medium, there is catalyzed reaction, emit the H that reducing power is very strong
-, as shown in the formula:
H
2PO
2 -+OH
-→H
2PO
3 -+H
-
Ni
2+by H, reduced, suc as formula:
Ni
2++2H
-→(Ni
2++2H+2e)→Ni+H
2
In plating process, the side reaction of generation is:
2H
2PO
2 -+6H
-+4H
2O→2P+5H
2+8OH
-
Therefore, coating is deposited on Copper Powder Surface with the form of Ni-P alloy.Along with the carrying out of reaction, the catalytic activity of Copper Powder Surface reduces gradually, and Ni-P alloy is grown up with homophase forming core gradually in the deposition of Copper Powder Surface, obtains certain thickness coating nickel coated copper powder.
Therefore, plating process just can spontaneously not carried out under heating condition in room temperature, the powder coating that obtains more even, continuous than other preparation method's coating, bonding force is strong, simultaneously technique simple, reduce plating cost.
Pre-treatment and the integrated plating technic of plating process that this patent adopts, can obtain coated nickel coated copper powder completely in room temperature, compares independent pre-treating technology and non-room temperature process, both saved the water resources of pretreatment cleaning powder, saved again energy consumption.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow process of nickel coated copper powder of the present invention;
Fig. 2 is the microscopic appearance (30wt.%) of the nickel coated copper powder prepared of the present invention;
Fig. 3 is the section pattern of the nickel coated copper powder of the different Ni contents prepared of the present invention;
Fig. 4 is the magnetic property of the nickel coated copper powder prepared of the present invention;
Fig. 5 is the microscopic appearance (40wt.%) of the spherical nickel coated copper powder prepared of the present invention;
Fig. 6 is nickel coated copper powder conductive rubber effectiveness of shielding under different frequency range prepared by the present invention.
Embodiment
Below in conjunction with some examples, preparation method of the present invention is further described.
Example 1
Component design nickel content is 30%, copper powder quality 2g, and diameter of particle is 75 μ m.Electroplate liquid formulation: single nickel salt 39g/L, sodium hypophosphite 40g/L, Trisodium Citrate 44g/L, copper powder heap(ed) capacity is 20g/L.Latter stage, plating solution volume was about 100ml, plating pH=12～13, and preparation technology's flow process is as shown in Figure 1.
Take a
1=a
2=2.0g sodium hydroxide, dissolves to obtain A
1, A
2; Measure B
1=10ml, B
2=2ml; Mixed solution A
2with B
2, obtain solution C ≈ 20ml, wherein a
2in C, concentration is 100g/L, B
2in C, concentration is 100ml/L; By A
1, copper powder, B
1slowly add successively in plating solution beaker, do not stop to stir plating solution; The plating reaction times is 10～20min, in plating process, slowly drips C solution 20～30min, and mean rate is 1～2ml/min, makes bath pH value maintain (12～13); After plating solution clarification, continue to stir 10min; After powder is uniformly dispersed, stop stirring standing, filtration; After cleaning successively with clear water and dehydrated alcohol, after 80 ℃ of vacuum-drying 10h, obtain 3.02g nickel coated copper powder.
It is completely coated that gained powder reaches, and microscopic appearance as shown in Figure 2; Approximately 1 micron of thickness of coating, as shown in Fig. 3-a; The powder specific magnetising moment reaches 10emu/g, as Fig. 4; 150 ℃ of atmospheric oxidns 240 hours, weightening finish 0.002%(copper powder weightening finish 0.30%)≤0.01%.
The lower coating EDS composition analysis of the different pH values of table 1
Example 2
Design example 1 simultaneous test, plating pH=11～12, other operate with example 1, and EDS Coating composition is analyzed as table 1.
Example 3
Design example 1 simultaneous test, plating pH=13～14, other operate with example 1, and EDS Coating composition is analyzed as table 1.
Example 4
Component design nickel content is 40%, and copper powder heap(ed) capacity is 20g/L, and diameter of particle is 75 μ m.Electroplate liquid formulation: single nickel salt 60g/L, sodium hypophosphite 55g/L, Trisodium Citrate 68g/L.Copper powder quality 2g, latter stage, plating solution volume was about 100ml, plating pH=12～13, preparation technology's flow process is as shown in Figure 1.
The preparation of pH value conditioning agent and operation steps are with example 1.
The final 3.58g nickel coated copper powder that obtains, it is completely coated that powder reaches, and thickness of coating is as shown in Fig. 3-b; The powder specific magnetising moment reaches 11emu/g,, as Fig. 4; 150 ℃ of atmospheric oxidns 240 hours, weightening finish 0.002%(copper powder weightening finish 0.30%).
Example 5
The spherical copper powder preparation formula that design nickel content is 40%, copper powder heap(ed) capacity is 20g/L, diameter of particle is 45 μ m.Electroplate liquid formulation: single nickel salt 60g/L, sodium hypophosphite 55g/L, Trisodium Citrate 68g/L.Copper powder quality 2g, latter stage, plating solution volume was about 100ml, plating pH=12～13, preparation technology's flow process is as shown in Figure 1.
Other experimental implementation are with example 4, and it is completely coated that powder reaches, and microscopic appearance as shown in Figure 5.
Example 6
Component design nickel content is 30%, and copper powder heap(ed) capacity is 20g/L, and diameter of particle is 75 μ m.Electroplate liquid formulation: single nickel salt 39g/L, sodium hypophosphite 40g/L, Trisodium Citrate 44g/L.Copper powder quality 200g, latter stage, plating solution volume was about 10L, plating pH=12～13, preparation technology's flow process is as shown in Figure 1.
Take a
1=200g, a
2=100g sodium hydroxide, dissolves to obtain A
1, A
2; Measure B
1=800ml, B
2=160ml, obtains solution C ≈ 400ml, wherein a
2in C, concentration is 250g/L, B
2in C, concentration is 80ml/L; By A
1, copper powder, B
1slowly add successively in plating solution beaker, do not stop to stir plating solution; The plating reaction times is 30～40min, in plating process, slowly drips C solution 40～60min, and mean rate is 6～10ml/min, makes bath pH value maintain (12～13); After plating solution clarification, continue to stir 60min; After powder is uniformly dispersed, stop stirring standing, filtration; After cleaning successively with clear water and dehydrated alcohol, after 80 ℃ of vacuum-drying 12h, obtain 150 ℃ of atmospheric oxidns of 294g nickel coated copper powder 240 hours, weightening finish≤0.005%(copper powder weightening finish 0.30%).
Example 7
Component design nickel content is 40%, and copper powder heap(ed) capacity is 20g/L, and diameter of particle is 75 μ m.Electroplate liquid formulation: single nickel salt 60g/L, sodium hypophosphite 55g/L, Trisodium Citrate 68g/L.Copper powder quality 200g, latter stage, plating solution volume was about 10L, plating pH=12～13, preparation technology's flow process is as shown in Figure 1.
The preparation of pH value conditioning agent and operation steps are with example 6.
The final 342g nickel coated copper powder that obtains, 150 ℃ of atmospheric oxidns 240 hours, weightening finish≤0.005%(copper powder increases weight 0.30%).
Example 8
Component design nickel content is 30%, and copper powder heap(ed) capacity is 33.3g/L, and diameter of particle is 75 μ m.Electroplate liquid formulation: single nickel salt 65g/L, sodium hypophosphite 60g/L, Trisodium Citrate 100g/L.Copper powder quality 500g, latter stage, plating solution volume was about 10L, plating pH=11～13, preparation technology's flow process is as shown in Figure 1.
Take a
1=300g, a
2=150g sodium hydroxide, dissolves to obtain A
1, A
2; Measure B
1=1500ml, B
2=300ml, obtains solution C ≈ 500ml, wherein a
2in C, concentration is 300g/L, B
2in C, concentration is 80ml/L; By A
1, copper powder, B
1slowly add successively in plating solution beaker, do not stop to stir plating solution; The plating reaction times is 30～40min, in plating process, slowly drips C solution 40～60min, and mean rate is 8～12ml/min, makes bath pH value maintain (11～13); After plating solution clarification, continue to stir 60min; After powder is uniformly dispersed, stop stirring standing, filtration; After cleaning successively with clear water and dehydrated alcohol, 80 ℃ of vacuum-drying 12h, obtain 725g nickel coated copper powder.150 ℃ of atmospheric oxidns 240 hours, weightening finish≤0.005%(copper powder weightening finish 0.30%).
Example 9
Component design nickel content is 40%, and copper powder heap(ed) capacity is 33.3g/L, and diameter of particle is 75 μ m.Electroplate liquid formulation: single nickel salt 100g/L, sodium hypophosphite 80g/L, Trisodium Citrate 100g/L.Copper powder quality 500g, latter stage, plating solution volume was about 10L, plating pH=11～13, preparation technology's flow process is as shown in Figure 1.
The preparation of pH value conditioning agent and operation steps are with example 8.
The final 850g nickel coated copper powder that obtains.150 ℃ of atmospheric oxidns 240 hours, weightening finish≤0.005%(copper powder weightening finish 0.30%).
Example 10
Component design nickel coated copper powder conductive rubber, filler nickel coated copper powder quality is filled 220 parts, nickel content 30%.
Take silica-based glue 100g, nickel coated copper powder 220g; Filler slowly, is repeatedly added to base glue, uniform stirring 30min, vacuum stripping 30min; (120～150) ℃ sulfuration (5～10) min, the conductive rubber slice of acquisition 15 * 15 * 2mm.Adopt the effectiveness of shielding of coaxial method testing conductive rubber under different frequency range as shown in Figure 6.Under medium-high frequency, the effectiveness of shielding of conductive rubber is good, and under 100MHz, effectiveness of shielding is more than 48dB; Under 500MHz, effectiveness of shielding is more than 51dB; Under 1GMHz, effectiveness of shielding is more than 56dB; Under 1.5GHz, effectiveness of shielding is more than 58dB.Therefore, nickel coated copper powder is applicable to electromagnetic shielding conductive rubber, has good effectiveness of shielding.
Claims (10)
1. the preparation method of nickel coated copper powder for conductive rubber, is characterized in that, by reasonable preparation plating solution and pH adjusting agent, the stable pH value of controlling, make copper powder pre-treatment and plating process integrated, stablize plating process, comprise the following steps:
(1) pH value conditioning agent preparation: take two parts of sodium hydroxide a
1, a
2, be configured to respectively solution A
1, A
2; Measure two parts of strong aqua B
1, B
2; By B
2add A
2in, stir, be designated as solution C;
(2) plating solution preparation: take single nickel salt, Trisodium Citrate, sodium hypophosphite, add in deionized water and dissolve, do not stop to stir, each component is fully dissolved, obtain plating solution;
(3) plating process: under stirring at room condition, by the A in step (1)
1solution slowly adds in the plating solution of step (2); Take copper powder, gradually copper powder is joined in plating solution, copper powder is uniformly dispersed; Add gradually subsequently B
1, do not stop to stir; In plating process, solution C is continuously added drop-wise in system, bath pH value is tended towards stability; In the plating later stage, plating solution clarification, powder gray, continue to stir, until powder is uniformly dispersed, nothing is reunited, stops stirring;
(4) post-processed: powder is sedimentation completely in plating solution, removes plating solution, obtains nickel coated copper powder; Adopt clear water to clean powder to neutral, then use soaked in absolute ethyl alcohol; Last vacuum-drying obtains nickel-plated copper powder;
Above-mentioned steps (1) sodium hydroxide: a
2=(0.5～1) a
1, B
2=(0.2～0.5) B
1, strong aqua is (25～28) wt.%, a in above-mentioned steps (1) solution C
2consumption be 100～300g/L, B
2consumption be 80～100ml/L; Above-mentioned steps (3) sodium hydroxide a
1concentration in plating solution is 10g～40g/L; Step (3) B
1consumption in plating solution is 10～150ml/L, in step (3): the mol ratio of single nickel salt, sodium hypophosphite, Trisodium Citrate is 1:(1～3): (0.5～1); Copper powder consumption is that 20～33.3g/L, concentration of nickel sulfate are that 23～100g/L, sodium hypophosphite concentration are that 28～100g/L, sodium citrate concentration are 26～110g/L; In above-mentioned steps (3), copper powder particle size is 45～75 μ m, and pattern is dendroid or spherical.
2. according to the method for claim 1, it is characterized in that rapid (3) sodium hydroxide a
1concentration in plating solution is 20g/L.
3. according to the method for claim 1, it is characterized in that step (3) B
1consumption in plating solution is 80～100ml/L.
4. according to the method for claim 1, it is characterized in that, the continuous time for adding of above-mentioned steps (3) preferred solution C is to be 20～60min in the plating reaction times, drop rate is (1～12) ml/min, after step (3) drips B1 and the pH that drips plating solution in the process of C keep stablizing pH=11～14.
5. according to the method for claim 4, it is characterized in that, after step (3) drips B1 and the pH that drips plating solution in the process of C keep stablizing pH=12～13.
6. according to the method for claim 1, it is characterized in that, above-mentioned steps (3) drips the process of solution C, changes into and drips continuously separately A simultaneously
2with B
2.
7. according to the method for claim 1, it is characterized in that, if make in advance nickel content 30wt.% in the finished product, the formula of step (3): the total mass≤200g of copper powder, copper powder 20g/L, single nickel salt 39g/L, sodium hypophosphite 40g/L, Trisodium Citrate 44g/L in plating solution; If copper powder total mass >200g, copper powder 33.3g/L, single nickel salt 65g/L, sodium hypophosphite 60g/L, Trisodium Citrate 100g/L in plating solution.
8. according to the method for claim 1, it is characterized in that, if make in advance nickel content 40wt.% in the finished product, the formula of step (3): the total mass≤200g of copper powder, copper powder 20g/L, single nickel salt 60g/L, sodium hypophosphite 55g/L, Trisodium Citrate 68g/L in plating solution; The total mass >200g of copper powder, copper powder 33.3g/L, single nickel salt 100g/L, sodium hypophosphite 80g/L, Trisodium Citrate 100g/L in plating solution.
9. according to the method for claim 1, it is characterized in that, step (4) is cleaned, is protected with dehydrated alcohol or acetone, soaks 5～10min.
10. according to the method for claim 1, it is characterized in that, step (4) vacuum-drying temperature is (80～100) ℃, and the time is (10～12) h.
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| CA2574173A1 (en) * | 2004-07-22 | 2006-01-26 | Mitsui Mining & Smelting Co., Ltd. | Nickel coated copper powder and process for producing the same |
| CN1817521A (en) * | 2006-03-17 | 2006-08-16 | 金川集团有限公司 | Production of composite copper powder with nickle coating |
| CN1876282A (en) * | 2006-07-07 | 2006-12-13 | 清华大学 | Chemical method for silver coating on copper powder surface |
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| CA2574173A1 (en) * | 2004-07-22 | 2006-01-26 | Mitsui Mining & Smelting Co., Ltd. | Nickel coated copper powder and process for producing the same |
| EP1795284A1 (en) * | 2004-07-22 | 2007-06-13 | Mitsui Mining & Smelting Co., Ltd. | Nickel coated copper powder and process for producing the same |
| CN1988973A (en) * | 2004-07-22 | 2007-06-27 | 三井金属矿业株式会社 | Nickel coated copper powder and process for producing the same |
| CN1817521A (en) * | 2006-03-17 | 2006-08-16 | 金川集团有限公司 | Production of composite copper powder with nickle coating |
| CN1876282A (en) * | 2006-07-07 | 2006-12-13 | 清华大学 | Chemical method for silver coating on copper powder surface |
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