CN1440951A - Continuous chemical powder plating method and apparatus - Google Patents
Continuous chemical powder plating method and apparatus Download PDFInfo
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- CN1440951A CN1440951A CN 03115963 CN03115963A CN1440951A CN 1440951 A CN1440951 A CN 1440951A CN 03115963 CN03115963 CN 03115963 CN 03115963 A CN03115963 A CN 03115963A CN 1440951 A CN1440951 A CN 1440951A
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Abstract
The present invention discloses a continuous chemical powder-plating method and apparatus. The apparatus incldues the first container with suspension comprising powder and solution L1, mechanical stirrer or ultrasonic generator inside the first container, the second container with solution L2, with the solution L1 and solution L2 being main salt and reducing liquid separately or plating liquid and pH regulating liquid separately. The first container and the second container are connected to a mixing chamber via pipe with separate metering pump, the mixing chamber is connected via pipe to coil pipe in the ultrasonic generator, and the coil pipe is also connected to one third container. After the solution L1 and the solution L2 are mixed in certain ratio, the mixed solution is set in the coil pipe for chemical plating reaction.
Description
Technical field
The present invention relates to a kind of continuous powdery chemical plating method and device thereof.
Background technology
Electroless plating is to utilize appropriate reductant that the solution metal ion is reduced on the surface of tool catalytic activity selectively to separate out, and forms a kind of chemical treatment method of metal plating.In the powder surface electroless plating, can obtain composite granules such as metallic cover pottery, polymer, metal, in fields such as electrocondution slurry, electrical contact material, stealth material, sintex, hot spray powder, be widely used.
During powder electroless, the homogeneity of metallic cover is a crucial difficult problem.Adopt the method for low-temperature ultrasonic electroless plating, solved powder, especially cladding uniformity problem (number of patent application 01116714.9) during the superfine powder electroless plating preferably.But the used container of this method is less, still has the uneven problem of different powder surface metal thickness when producing in batches.This is that inhomogeneous as the coating of initial metal, then these powders that coated can preferentially be grown up fast because electroless plating is self-catalyzed reaction.And the amount of plating bath is many when producing in batches, therefore can provide the amount of metal ion of separating out many, thereby make the non-uniform phenomenon of metallic cover more serious.
Powder electroless carries out in small containers usually, adds a certain amount of powder in plating bath, makes it to react, and question response finishes back separation solution and powder, this method can only performance period the production of formula.Day the present invention a kind of new electroless plating technology " method of dripping ", and designed a kind of specific equipment, applied for relevant patent (the clear 62-30885 of special Open (1987), the flat 1-242782 of special Open (1989), special fair 2-25431 (1990)).It is at first powder to be made suspension in the aqueous solution, and quantitative respectively adding become owner of salt and reduced liquid in this container while stirring.Its main purpose is the self-decomposition that prevents plating bath.From this method, can't solve the homogeneity of metallic cover when producing in batches at all, and can not realize serialization production.
Summary of the invention
The object of the present invention is to provide a kind of continuous powdery chemical plating method and device thereof, improve the homogeneity of metallic cover thickness between different powders and realized the serialization of electroless plating process.
The technical solution used in the present invention is as follows:
1, principle
When considering on the different powder surfaces metallic cover thickness evenness, the ideal method is around each powder corresponding with it plating bath amount to be arranged, and so many metal ions can only be provided from this plating bath.For this reason, adopt special equipment, mixing zone and reaction zone are set, and make the solution that contains powder, in specific time, pass through reaction zone, as shown in Figure 1 with small amount.Like this, respectively at time t1, t2, t3 ... solution L1, L2, the L3 of ti input pipe ... between the Li, because the restriction of caliber, the mixing of each solution is controlled in the as far as possible little scope, and the metal that the result just can make powder surface separate out only limits to this small quantity solution metal ion.
2, method
1) at first container pack into powder and solution L
1Suspension, stir or ultrasonic generator by mechanical stirrer, or adopt macromolecule dispersing agent to make powder that sedimentation not take place simultaneously;
2) the solution L that in first container, packs into
2
3) L
1/ L
2Be respectively that main salt/reduced liquid or reduced liquid/main salts solution or plating bath/pH adjusts liquid or pH adjusts liquid/plating bath.
4) volume pump by separately respectively with two kinds of solution in first container and second container, the input mixing section, the pH value that makes mixed solution in proportion is 4.5～13.5;
5) under the ultrasonic wave radiation, flow through coil pipe from the mixed solution of mixing section output by the coil pipe that places ultrasonic generator and carry out electroless plating reaction;
6) powder after reaction finishes and plating bath flow out from outlet and enter the 3rd container.
3, silicon nitride or the powders such as aluminum oxide or silicon oxide or zirconium white or titanium carbide or zinc oxide or stannic oxide or diamond with nanometer or micron-scale add in the preprocessing solution, under the room temperature, apply ultrasonication respectively at alligatoring, sensitization, activation stage, clean the back oven dry;
Metallic cover is handled and is used bath composition:
Main salt: single nickel salt or rose vitriol or copper sulfate or Silver Nitrate 10～50 grams per liters
Reductive agent: formaldehyde 2～50 grams per liters of inferior sodium phosphate or 38% concentration
Complexing agent: Trisodium Citrate or disodium ethylene diamine tetraacetate or
Ammoniacal liquor 10～50 grams per liters of 25% concentration
PH buffer reagent: boric acid or sodium-acetate 0～50 grams per liter
Dispersion agent: 0～100 milliliter/liter of methyl alcohol
Stablizer: thiocarbamide or yellow prussiate of potash 0～50 mg/litre
PH regulator agent: sodium hydroxide or sulfuric acid 0～30 grams per liter
Water adds to into 1 liter
The preparation method:
The medicine of above-mentioned composition is mixed with solution L respectively
1And L
2, then that oneself is pretreated nanometer or micro-powder add and contain solution L
1Container 1, with solution L
2Put into container 2, L
1/ L
2Be respectively that main salts solution/reduced liquid or reduced liquid/main salts solution or plating bath/pH adjusts liquid or pH adjusts liquid/plating bath.It is 4.5～13.0 that two kinds of solution mix back pH, coats in temperature is 20～60 ℃, ultrasonic wave, gained powder in the container 3 is separated with plating bath, and through cleaning and the aftertreatment of oven dry gets final product.
4, device
It comprises: first container of dress suspension, mechanical stirrer or ultrasonic generator are housed in first container, adorn second container of general solution, first container and second container connect the mixing section mixing section through separately pipe, separately volume pump respectively and are connected to the coil pipe of the ultrasonic generator of packing into through pipe, and coil pipe inserts the 3rd container through pipe.
The useful effect that the present invention has is:
It is compared with general powder electroless, owing to adopt a kind of continuous powdery chemical plating method and device thereof, has improved the homogeneity of metallic cover thickness between different powders.In addition, also realized the serialization of electroless plating process, reduced labour intensity, improved the consistence of production efficiency and quality product.The present invention can be used for applying hyperacoustic electroless plating, also is applicable to conventional electroless plating.
Description of drawings
Fig. 1 is a continuous powdery electroless plating schematic diagram;
Fig. 2 is the structural representation of apparatus of the present invention.
Embodiment
As shown in Figure 2, the present invention includes powder and solution L are housed
1First container 1, mechanical stirrer or ultrasonic generator 3 are housed in first container 1, solution L is housed
2Second container, 2, the first containers 1 and second container 2 connect mixing section 6 through pipe separately, volume pump 4,5 separately respectively, mixing section 6 is connected to the coil pipe 7 of the ultrasonic generator 8 of packing into through pipe, coil pipe 7 inserts the 3rd container 9 through pipe.
1, plating bath is divided into two portions, a part is powder and solution L
1, another part is solution L
2Pack in container 1 and 2.
2, solution L
1/ L
2Be respectively that main salts solution/reduced liquid or reduced liquid/main salts solution or plating bath/pH adjusts liquid or pH adjusts liquid/plating bath.
3, the suspension in the container 1 stirs by mechanical stirrer 3 or ultrasonic generator, also can adopt macromolecule dispersing agent etc. to make powder that sedimentation not take place simultaneously.
4, two solution are passed through volume pump 4 and 5, quantitatively import mixing section 6 according to a certain percentage, make two kinds of solution in the microcosmic scope, realize mixing.
5, mixing section can be static mixer, the mixing tank that also can constitute with twisted tube and high speed rotating atomizing mixer etc.
6, mixed solution is exported from mixing section, and by the coil pipe 7 of certain diameter, certain-length, coil pipe places ultrasonic generator 8.Under ultrasonic irradiation, plating bath flows through coil pipe with certain flow velocity, in specific time, carries out electroless plating reaction.Coil pipe can be a glass, also can be inflexible plastics class material.
7, powder and plating bath after reaction finishes flow out from outlet, enter container 9.
In this process, the caliber of coil pipe plays a decisive role to the phase mutual interference that prevents mixed solution, thereby guarantees the homogeneity of each batch powder clad metal thickness; The length of flow and coil pipe has determined the time of reaction.By aforesaid device, can also realize the full-automatic operation of whole process.
Embodiment 1
1) caliber is 20 millimeters, 7.2 liters/hour of flow velocitys, and 12 meters of ultrasonic wave inner disc pipe ranges, then the time of solution under ultrasonic irradiation is 90 minutes, per hour the raw material powder scale of construction is 648 grams.
2) volume pump power, specification: 600W, 10 liters/hour
3) ultrasonic power, frequency are: 300W, 20～40KHz
4) composite granule: 720 Grams Per Hours (metal content is in weight percent 10%)
5) solution composition: nano alumina powder jointed, be of a size of 10～20nm.Powder after sensitization, activation adds sulfur acid cobalt 35 grams per liters, and Trisodium Citrate 15 grams per liters in the main salts solution of boric acid 40 grams per liters, stir and form suspension L
1Another solution L
2Receive 20 grams per liters by ortho phosphorous acid, and a certain amount of NaOH forms the pH value 10.5 of mixed solution.The gained composite granule is even compound cobalt/aluminum oxide powder under the nano-scale through the projection electron microscopic observation.
Embodiment 2
1) caliber is 20 millimeters, 35 liters/hour of flow velocitys, and 60 meters of ultrasonic wave inner disc pipe ranges, the time of solution under ultrasonic irradiation is 90 minutes, per hour the raw material powder scale of construction is 3240 grams.
2) volume pump power, specification: 3000W, 50 liters/hour
3) ultrasonic power, frequency are: 1500W, 20～40KHz
4) composite granule: 6480 Grams Per Hours (metal content is in weight percent 50%)
5) solution composition: the micron titanium oxide powder is of a size of 0.8～1.2 μ m.Powder after sensitization, activation adds and to contain ortho phosphorous acid and receive 15 grams per liters, and the reduced liquid L of a certain amount of H2SO4
1In, stir and form suspension; Another solution is single nickel salt 30 grams per liters, Trisodium Citrate 17 grams per liters, the main saline solution L of sodium-acetate 15 grams per liters
2, the pH value 4.5 of mixed solution.The result is by scanning electron microscopic observation, and nickel evenly is coated on the carbonized titanium powder surface.
Embodiment 3
1) caliber is 20 millimeters, 7.2 liters/hour of flow velocitys, and 12 meters of ultrasonic wave inner disc pipe ranges, the time of solution under ultrasonic irradiation is 30 minutes, per hour the raw material powder scale of construction is 648 grams.
2) volume pump power, specification: 600W, 10 liters/hour
3) ultrasonic power, frequency are: 300W, 20～40KHz
4) composite granule: 1296 Grams Per Hours (metal content is in weight percent 50%)
5) solution composition: micron stannic oxide powder is of a size of 1～5 μ m.Powder after sensitization, activation adds and contains formaldehyde 6 grams per liters, the reduced liquid L that methyl alcohol is 2.2 milliliters/liter
1In, stir and form suspension; Another solution L
2By Silver Nitrate 17.5 grams per liters, ammoniacal liquor 35 grams per liters, sodium hydroxid 2 grams per liters are formed.The gained composite granule evenly is compounded in the powder of putty powder surface through scanning electron microscopic observation for Ag.
Embodiment 4
1) caliber is 10 millimeters, 35 liters/hour of flow velocitys, and 60 meters of ultrasonic wave inner disc pipe ranges, the time of solution under ultrasonic irradiation is 30 minutes, per hour the raw material powder scale of construction is 324 grams.
2) volume pump power, specification: 3000W, 50 liters/hour
3) ultrasonic power, frequency are: 1500W, 20～40KHz
4) composite granule: 3240 Grams Per Hours (metal content is in weight percent 90%)
5) solution composition: the micron silica powder is of a size of 5～10 μ m.Powder after sensitization, activation adds and to contain hydroxide and receive the pH value adjustment liquid L of 20 grams per liters
1In, stir and form suspension; Another solution is by copper sulfate 44 grams per liters, disodium ethylene diamine tetraacetate 66 grams per liters, yellow prussiate of potash 10 mg/litre, 24 milliliters/liter in formaldehyde, the plating bath L that methyl alcohol is 100 milliliters/liter
2Form, mix the pH value 13.0 of back solution.The gained powder is through scanning electron microscopic observation, and copper evenly is coated on the silica powder surface.
Claims (4)
1. continuous powdery chemical plating method is characterized in that:
1) at first container pack into powder and solution L
1The suspension of making stirs or ultrasonic generator by mechanical stirrer, or adopts macromolecule dispersing agent to make powder that sedimentation not take place simultaneously;
2) the solution L that in second container, packs into
2
3) solution L
1/ L
2Be respectively that main salts solution/reduced liquid or reduced liquid/main salts solution or plating bath/pH adjusts liquid or pH adjusts liquid/plating bath;
4) volume pump by separately respectively with two kinds of solution in first container and second container, the input mixing section, the pH value that makes mixed solution in proportion is 4.5～13.5;
5) under the ultrasonic wave radiation, flow through coil pipe from the mixed solution of mixing section output by the coil pipe that places ultrasonic generator and carry out electroless plating reaction;
6) powder after reaction finishes and plating bath flow out from outlet and enter the 3rd container.
2. a kind of continuous powdery chemical plating method according to claim 1 is characterized in that:
1) silicon nitride or the powders such as aluminum oxide or silicon oxide or zirconium white or titanium carbide or zinc oxide or stannic oxide or diamond with nanometer or micron-scale add in the preprocessing solution, under the room temperature, apply ultrasonication respectively at alligatoring, sensitization, activation stage, clean the back oven dry;
2) metallic cover is handled and is used bath composition:
Main salt: single nickel salt or rose vitriol or copper sulfate or Silver Nitrate 10～50 grams per liters
Reductive agent: formaldehyde 2～50 grams per liters of inferior sodium phosphate or 38% concentration
Complexing agent: Trisodium Citrate or disodium ethylene diamine tetraacetate or
Ammoniacal liquor 10～50 grams per liters of 25% concentration
PH buffer reagent: boric acid or sodium-acetate 0～50 grams per liter
Dispersion agent: 0～100 milliliter/liter of methyl alcohol
Stablizer: thiocarbamide or yellow prussiate of potash 0～50 mg/litre
PH regulator agent: sodium hydroxide or sulfuric acid 0～30 grams per liter
Water adds to into 1 liter
3) preparation method:
The medicine of above-mentioned composition is mixed with solution L respectively
1And L
2, nanometer that will be pretreated or micro-powder add and contain solution L then
1Container 1, with solution L
2Put into container 2, L
1/ L
2Be respectively that main salts solution/reduced liquid or reduced liquid/main salts solution or plating bath/pH adjusts liquid or pH adjusts liquid/plating bath.It is 4.5～13.0 that two kinds of solution mix back pH, coats in temperature is 20～60 ℃, ultrasonic wave, gained powder in the container 3 is separated with plating bath, and through cleaning and the aftertreatment of oven dry gets final product.
3. the device of a kind of continuous powdery chemical plating method according to claim 1, it is characterized in that it comprises: first container (1) of dress suspension, mechanical stirrer or ultrasonic generator (3) are housed in first container (1), adorn second container (2) of general solution, first container (1) connects mixing section (6) through pipe separately, volume pump (4,5) separately respectively with second container (2), mixing section (6) is connected to the coil pipe (7) of the ultrasonic generator of packing into (8) through pipe, and coil pipe (7) inserts the 3rd container (9) through pipe.
4. the device of a kind of continuous powdery chemical plating method according to claim 3 is characterized in that: said mixing section (6) is static mixer or the mixing tank or the high speed rotating atomizing mixer that are made of twisted tube.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03115963XA CN1176873C (en) | 2003-03-20 | 2003-03-20 | Continuous chemical powder plating method and apparatus |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03115963XA CN1176873C (en) | 2003-03-20 | 2003-03-20 | Continuous chemical powder plating method and apparatus |
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| Publication Number | Publication Date |
|---|---|
| CN1440951A true CN1440951A (en) | 2003-09-10 |
| CN1176873C CN1176873C (en) | 2004-11-24 |
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104066535A (en) * | 2012-01-17 | 2014-09-24 | 同和电子科技有限公司 | Silver-coated copper alloy powder and method for manufacturing same |
| CN104060245A (en) * | 2014-06-10 | 2014-09-24 | 上海交通大学 | Super-hydrophobic nano-silver raman-enhanced substrate material and preparation method thereof |
| CN104498916A (en) * | 2014-11-24 | 2015-04-08 | 广西大学 | Method used for preparing aluminium-doped zinc oxide thin film via electroless deposition |
| CN104846411A (en) * | 2015-04-27 | 2015-08-19 | 北京航空航天大学 | Method for preparing flowerlike nanometer cobalt by using anodised aluminum template, and product of same |
| CN106077623A (en) * | 2016-07-19 | 2016-11-09 | 仇颖莹 | A kind of preparation method being evenly coated copper-coated iron composite powder |
| CN106435541A (en) * | 2016-09-26 | 2017-02-22 | 四川大学 | Aluminium alloy grain refiner based on titanium carbonitride, and preparation method thereof |
| CN106898748A (en) * | 2017-03-17 | 2017-06-27 | 成都新柯力化工科技有限公司 | A kind of preparation method of the ternary lithium nickel cobalt manganese battery electrode material of core-shell structure |
| CN107267965A (en) * | 2017-07-31 | 2017-10-20 | 北京矿冶研究总院 | Continuous type powder chemical plating device |
| CN110802224A (en) * | 2018-08-06 | 2020-02-18 | 三菱电机株式会社 | Preparation method of silver-nickel-tin oxide composite powder and silver-nickel-tin oxide electrical contact material |
| CN114737175A (en) * | 2022-06-13 | 2022-07-12 | 常州金襄新材料科技有限公司 | Silver-coated copper powder continuous conveying device |
-
2003
- 2003-03-20 CN CNB03115963XA patent/CN1176873C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104066535A (en) * | 2012-01-17 | 2014-09-24 | 同和电子科技有限公司 | Silver-coated copper alloy powder and method for manufacturing same |
| CN104066535B (en) * | 2012-01-17 | 2016-11-09 | 同和电子科技有限公司 | Silver coated copper alloy powder and production method thereof |
| CN104060245A (en) * | 2014-06-10 | 2014-09-24 | 上海交通大学 | Super-hydrophobic nano-silver raman-enhanced substrate material and preparation method thereof |
| CN104498916B (en) * | 2014-11-24 | 2017-04-26 | 广西大学 | Method used for preparing aluminium-doped zinc oxide thin film via electroless deposition |
| CN104498916A (en) * | 2014-11-24 | 2015-04-08 | 广西大学 | Method used for preparing aluminium-doped zinc oxide thin film via electroless deposition |
| CN104846411B (en) * | 2015-04-27 | 2017-08-25 | 北京航空航天大学 | The method and its product of flower-like nanometer metal cobalt are prepared using anodic oxidation aluminium formwork |
| CN104846411A (en) * | 2015-04-27 | 2015-08-19 | 北京航空航天大学 | Method for preparing flowerlike nanometer cobalt by using anodised aluminum template, and product of same |
| CN106077623A (en) * | 2016-07-19 | 2016-11-09 | 仇颖莹 | A kind of preparation method being evenly coated copper-coated iron composite powder |
| CN106435541A (en) * | 2016-09-26 | 2017-02-22 | 四川大学 | Aluminium alloy grain refiner based on titanium carbonitride, and preparation method thereof |
| CN106435541B (en) * | 2016-09-26 | 2019-02-19 | 四川大学 | A kind of aluminum grain refiner and preparation method thereof based on titanium carbonitride |
| CN106898748A (en) * | 2017-03-17 | 2017-06-27 | 成都新柯力化工科技有限公司 | A kind of preparation method of the ternary lithium nickel cobalt manganese battery electrode material of core-shell structure |
| CN107267965A (en) * | 2017-07-31 | 2017-10-20 | 北京矿冶研究总院 | Continuous type powder chemical plating device |
| CN110802224A (en) * | 2018-08-06 | 2020-02-18 | 三菱电机株式会社 | Preparation method of silver-nickel-tin oxide composite powder and silver-nickel-tin oxide electrical contact material |
| CN114737175A (en) * | 2022-06-13 | 2022-07-12 | 常州金襄新材料科技有限公司 | Silver-coated copper powder continuous conveying device |
| CN114737175B (en) * | 2022-06-13 | 2022-08-12 | 常州金襄新材料科技有限公司 | Silver-coated copper powder continuous conveying device |
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| CN1176873C (en) | 2004-11-24 |
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