CN101709461B - Method for copper powder displacement for chemical silver plating - Google Patents
Method for copper powder displacement for chemical silver plating Download PDFInfo
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- CN101709461B CN101709461B CN2009101936978A CN200910193697A CN101709461B CN 101709461 B CN101709461 B CN 101709461B CN 2009101936978 A CN2009101936978 A CN 2009101936978A CN 200910193697 A CN200910193697 A CN 200910193697A CN 101709461 B CN101709461 B CN 101709461B
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Abstract
The invention discloses a method for displacement chemical silver plating on copper powder. The method comprises the following steps of: cleaning and oil removal, water washing, acid etching, water washing, catalytic liquid treating, chemical silver plating and the like. In the method, a catalytic liquid capable of preplanting catalytic mass points is developed; the surface of the copper powder is preplanted with discretely distributed palladium mass points after the copper powder is treated by the catalytic liquid at a room temperature by controlling components, pH value and treatment time of the catalytic liquid; and the preplanted palladium mass points can catalyze and promote the silver ion reduction to improve precipitation speed and to retard copper-ammonia complex ions to be absorbed on the copper surface so as to obtain a sliver plating layer with good cladding performance in the chemical silver-plating process for the copper powder. Compared with the conventional method of displacement chemical silver plating, the method realizes surface activation of the copper powder by pretreating the catalytic liquid, a silver content of the silver plating copper powder is greatly improved, the problems of poor cladding performance of replacement type chemical silver plating and the like are solved, and the method is simple in process and convenient to operate and has good application prospect.
Description
Technical field
The present invention relates to the copper powder process for treating surface, be specifically related to a kind of method of displacement chemical silver plating on copper powder; Use the silver-plated copper powder covering property of this method preparation good, can be widely used in various electromagnetic shielding fillers, conductive resin, the electrically conducting coating.
Background technology
The Cu-Ag metal powder can be widely used in fields such as electric slurry, electromagnetic shielding material and catalyzer.At present, preparation Cu-Ag metal powder comparison common chemical method has two kinds: a kind of is directly to make reductive agent with copper powder to remove to replace silver-colored ammonia coordination ion and obtain silver-colored particle, makes it to be deposited on the copper powder surface.This method is mainly adopted in present research, but this deposition majority all is to form to intersperse clad structure, copper cooperates ion that stronger adsorption is arranged to cuprammonium, hindered the further displacement of copper, the silver particle is slow at its surperficial forming core, be difficult to form successive coating, just form the structure of isolated island shape, cause coating imprecision in some part; Another kind is to adopt reductive agent silver ions to be restored the method for electroless plating from plating bath, other active atomics on the copper powder surface are the forming core catalytic center with copper atom or absorption, make silver-colored particle on the copper powder surface gradually nucleation grow up, thereby obtain the coating of covering continuously, but the less stable of plating bath, especially in the plating bath that some strong reductants (formaldehyde, hydrazine hydrate etc.) exist, lost efficacy easily and decompose, and electroless plating reaction speed is fast, is not easy to control.
(material protection, 2006,39 (9): then be to adopt the method for the copper powder chemical silvering of reductive agent such as glucose 28), go out the science and engineering skill before adopting activation and sensitization etc. before the plating, technology is complexity for document.Patent of invention (patent No. 02139151.3) discloses the preparation method of the high silver-plated copper powder of a kind of electric conductivity, but the covering property of not mentioned silver-plated copper powder in the literary composition, and silver content is the highest by only 30%, and plating bath need be heated to certain temperature.Application for a patent for invention (publication number CN101244459A) discloses the modifying function that utilizes rare earth, adopt the method for the auxiliary a kind of copper powder chemical silvering of ultrasonic wave in the process of copper powder plating front activating, sensitization and plating, institute's acquisition silvered film is evenly distributed, smooth surface, higher electric conductivity and oxidation-resistance are arranged, whether but whether contain a spot of rare earth metal cerium rare earth metal in the silvered film exists influence still to remain to be inquired into to the use of silver-plated copper powder, contain the formaldehyde composition in the plating bath, and operating procedure is loaded down with trivial details.Application for a patent for invention (publication number CN1876282A) is a kind of method that adopts glucose etc. for the copper powder chemical silvering of reductive agent, and silver-plated copper powder silver scope is 10%～20%, and content is lower.Application for a patent for invention (publication number CN101294281A) discloses the preparation method of the high silver-plated copper powder for low-temperature slurry of a kind of silver-plated efficient, but the silver-plated preceding copper powder of this method need carry out the ball milling slabbing.
Above-mentioned patent and document fail to solve chemical silvering substitution method solution composition complexity, covering property is poor, deficiencies such as the reduction method bath stability is poor, technology is more loaded down with trivial details, still exist that the silver-plated copper powder silver content is lower, problem such as the clad ratio that do not relate to silver-plated copper powder and antioxidant property, and then influence the stability and the reliability of silver-plated copper powder quality, application.
Summary of the invention
Cooperate ion that stronger adsorption is arranged at copper in the substitution method to cuprammonium, hindered the further displacement of copper, cause problems such as silvered film covering property difference.The chemical plating method that utilizes reductive agent that silver ions is restored from plating bath, problems such as the less stable of its plating bath carry out needing to carry out sensitization and activation before the chemical silvering, and operation is complicated.The advantage of the comprehensive two kinds of methods of the present invention, propose utilization and plant the strong simple substance palladium formation catalytic center of catalytic activity on the copper powder surface in advance, in silver plating liquid, promote the silver ion reduction deposition, hindering cuprammonium cooperates ion in the effect of copper surface adsorption, thereby obtain the silvered film of covering continuously, improved the compactness and the silver content of coating greatly, it is loaded down with trivial details to have solved other replacement ag plating method technologies, problems such as reductive agent silver impregnation method plating bath easily decomposes, not environmental protection.
The method of a kind of displacement chemical silver plating on copper powder provided by the invention comprises following steps:
1) gets copper powder earlier, the cleaning oil removing;
2) distilled water flushing, room temperature;
3) copper powder being added mass ratio is in 5～10% the diluted acid, to remove the oxide compound on copper powder surface;
4) distilled water flushing, room temperature;
5) catalytic liquid is handled, room temperature, and 1～30 minute, catalytic liquid was acidity or the basic solution that contains palladium salt 0.030～0.200g/L, after handling through catalytic liquid, planted discrete palladium particle in advance on the copper powder surface;
6) distilled water cleans repeatedly to filtrate and does not contain Cl
-Till the ion, room temperature;
7) room temperature is added in the copper powder after the activation in the silver nitrate solution that contains complexing agent, goes out fine and close silvered film at the copper powder surface reduction under the catalysis of palladium particle and condition of stirring;
8) reaction is finished after wash, cleans filter only in vacuum drying oven, dries down for 100 ℃ and promptly gets required silver-plated copper powder.
The dilute acid soln that the described acid etching of step 3) is used is one or more compound of sulfuric acid, nitric acid or phosphoric acid.
Palladium salt during the described catalytic liquid of step 5) is handled in the used catalytic liquid solution is one or more compound of Palladous chloride, dichloro diamino palladium, dichloro four ammonia palladiums.
Used catalytic liquid solution was acidity or basic solution during described step 5) catalytic liquid was handled, and wherein the acid in the acidic solution is one or more compound in lactic acid, acetic acid, oxysuccinic acid, citric acid, hydrochloric acid or the boric acid; Basic solution is an ammonia soln; The concentration of acid or ammoniacal liquor is 12～30g/L in the catalytic liquid.
The concentration of contained Silver Nitrate is 25～50g/L in the step 7) silver nitrate solution.
Contained complexing agent is one or more the mixture in Trisodium Citrate, sodium-acetate, Sodium.alpha.-hydroxypropionate, quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the ammoniacal liquor in the step 7) silver nitrate solution, and concentration is 60～130g/L.
The pH value of step 7) silver nitrate solution is 10～14.
The described stirring of step 7) is machinery, induction stirring and hyperacoustic one or both alr modes.
The beneficial effect of the invention is:
1. adopt treatment process of the present invention, before the chemical silvering copper powder being carried out catalytic liquid handles, active strong palladium becomes the forming core catalytic center on the copper powder surface, can improve activity, deposition uniformity and the covering property of silver ions displacement copper, under the situation of identical silver plating solution, silver content can improve 20%～500%, has improved the utilization ratio of plating bath greatly.
2. adopt treatment process of the present invention, after handling through catalytic liquid, when improving silver content, silver-colored clad ratio can reach more than 95%, has higher oxidation-resistance and electroconductibility.
3. adopt treatment process of the present invention, catalytic liquid is handled and is at room temperature carried out, and does not need heating.
4. adopt treatment process of the present invention, copper powder electroless plating silver plating solution is formed simple, does not contain the reductive agent that causes plating bath to decompose, and does not need heating in the plating process, at room temperature carries out bath stability.
Description of drawings
Fig. 1 is the silver-plated copper powder sem photograph of handling without catalytic liquid.
Fig. 2 is the silver-plated copper powder sem photograph of handling through catalytic liquid.
Comparison diagram 1 and Fig. 2, without the poor effect of the copper powder electroplate of surface active, coating is the structure of interspersing of isolated island formula, and the coating particle is thick among visible Fig. 1, the silver particles of absorption can't form successive coating.Can observe from Fig. 2, copper powder can prepare that the coating particle is tiny, even compact, the silver-plated copper powder that coats substantially fully after catalytic liquid is handled.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail.
Embodiment 1
1) under the room temperature 200 order copper powders is cleaned oil removing, distilled water flushing
2) use the salpeter solution that contains 5wt% under the room temperature, remove till the oxide compound on 75 grams, 200 purpose copper powder surfaces distilled water flushing;
3) will put into by containing the catalytic liquid that 0.035g/L Palladous chloride, 20g/L hydrochloric acid are formed through the copper powder of overpickling, and at room temperature, use distilled water to clean repeatedly to filtrate behind the treatment time 30min and do not contain Cl
-Till the ion;
4) configuration chemical silvering solution: the mixed twine mixture of the Silver Nitrate of 28g/L, 60g/L trisodium citrate and triethylene tetramine, use ammoniacal liquor and sodium hydroxide that the pH of silver plating solution is transferred to 10.5;
5) activated copper powder is put into silver plating solution, induction stirring reaction 20min
6) stop plating, with the silver-plated copper powder washing and filtering, at 100 ℃ of following vacuum dryings.
Gained silver-plated copper powder silver content is 17wt%, and clad ratio is 90%, and not activated prepared silver-plated copper powder silver content is 5wt%, and clad ratio is 43%.
Embodiment 2
1) under the room temperature 200 order copper powders is cleaned oil removing, distilled water flushing
2) use the sulphuric acid soln that contains 7wt% under the room temperature, remove till the oxide compound on 65 grams, 200 purpose copper powder surfaces distilled water flushing;
3) will put into by containing the catalytic liquid that 0.098g/L Palladous chloride, 25g/L hydrochloric acid and citric acid are formed through the copper powder of overpickling, and at room temperature, use distilled water to clean repeatedly behind the treatment time 20min and do not contain to the filtrate till the Cl-ion;
4) configuration chemical silvering solution: the mixed twine mixture of the Silver Nitrate of 34g/L, 110g/L Sodium.alpha.-hydroxypropionate and quadrol, use ammoniacal liquor and sodium hydroxide that the pH of silver plating solution is transferred to 12.5;
5) activated copper powder is put into silver plating solution, mechanical stirring reaction 20min
6) stop plating, with the silver-plated copper powder washing and filtering, at 100 ℃ of following vacuum dryings.
Gained silver-plated copper powder silver content is 23wt%, and clad ratio is 94%, and not activated prepared silver-plated copper powder silver content is 6wt%, and clad ratio is 48%.
Embodiment 3
1) under the room temperature 400 order copper powders is cleaned oil removing, distilled water flushing
2) use the phosphoric acid solution that contains 9.5wt% under the room temperature, remove till the oxide compound on 15 grams, 400 purpose copper powder surfaces distilled water flushing;
3) will put into by containing the activation solution that 0.130g/L dichloro four ammonia palladiums, 15g/L ammoniacal liquor are formed through the copper powder of overpickling, and at room temperature, use distilled water to clean repeatedly behind the treatment time 10min and do not contain to the filtrate till the Cl-ion;
4) configuration chemical silvering solution: the mixed twine mixture of the Silver Nitrate of 25g/L, 96g/L Sodium.alpha.-hydroxypropionate and tetraethylene pentamine, use ammoniacal liquor and sodium hydroxide that the pH of silver plating solution is transferred to 13;
5) activated copper powder is put into silver plating solution, machinery and the compound stirring reaction 20min of electromagnetism;
6) stop plating, with the silver-plated copper powder washing and filtering, at 100 ℃ of following vacuum dryings.
Gained silver-plated copper powder silver content is 44wt%, and clad ratio is 98%, and not activated prepared silver-plated copper powder silver content is 17wt%, and clad ratio is 65%.
Embodiment 4
1) under the room temperature 400 orders is cleaned oil removing, distilled water flushing
2) use phosphoric acid and the vitriolic solution that contains 8.5wt% under the room temperature, remove till the oxide compound on 40 grams, 400 purpose copper powder surfaces distilled water flushing;
3) will put into by containing the activation solution that 0.080g/L dichloro diamino palladium, 12g/L ammoniacal liquor are formed through the copper powder of overpickling, at room temperature, treatment time 5min;
4) the mixed twine mixture of Silver Nitrate, 106g/L Sodium.alpha.-hydroxypropionate, sodium-acetate and the diethylenetriamine of configuration chemical silvering solution 27g/L uses ammoniacal liquor and sodium hydroxide that the pH of silver plating solution is transferred to 13;
5) activated copper powder is put into silver plating solution, machinery and the compound stirring reaction 20min of ultrasonic wave;
6) stop plating, with the silver-plated copper powder washing and filtering, at 100 ℃ of following vacuum dryings.
Gained silver-plated copper powder silver content is 37wt%, and clad ratio is 96%, and not activated prepared silver-plated copper powder silver content is 11wt%, and clad ratio is 55%.
Embodiment 5
1) under the room temperature 400 order copper powders is cleaned oil removing, distilled water flushing
2) use nitric acid and the vitriolic solution that contains 6.5wt% under the room temperature, remove till the oxide compound on 30 grams, 400 purpose copper powder surfaces distilled water flushing;
3) will put into by containing the activation solution that 0.192g/L dichloro four ammonia palladiums, 20g/L ammoniacal liquor are formed through the copper powder of overpickling, and at room temperature, use distilled water to clean repeatedly to filtrate behind the treatment time 2min and do not contain Cl
-Till the ion;
4) the mixed twine mixture of Silver Nitrate, 126g/L trisodium citrate, sodium-acetate and the triethylene tetramine of configuration chemical silvering solution 48g/L uses ammoniacal liquor and sodium hydroxide that the pH of silver plating solution is transferred to 14;
5) activated copper powder is put into silver plating solution, induction stirring reaction 20min;
6) stop plating, with the silver-plated copper powder washing and filtering, at 100 ℃ of following vacuum dryings.
Gained silver-plated copper powder silver content is 56wt%, and clad ratio is 99%, and not activated prepared silver-plated copper powder silver content is 18wt%, and clad ratio is 75%.
Claims (8)
1. the method for a displacement chemical silver plating on copper powder is characterized in that this method comprises following steps:
1) gets copper powder earlier, the cleaning oil removing;
2) distilled water flushing, room temperature;
3) copper powder being added mass ratio is in 5～10% the diluted acid, to remove the oxide compound on copper powder surface;
4) distilled water flushing, room temperature;
5) catalytic liquid is handled, room temperature, and 1～30 minute, catalytic liquid was acidity or the basic solution that contains palladium salt 0.030～0.200g/L, after handling through catalytic liquid, planted discrete palladium particle in advance on the copper powder surface;
6) distilled water cleans repeatedly to filtrate and does not contain Cl
-Till the ion, room temperature;
7) room temperature is added in the copper powder after the activation in the silver nitrate solution that contains complexing agent, goes out fine and close silvered film at the copper powder surface reduction under the catalysis of palladium particle and condition of stirring;
8) reaction is finished after wash, cleans filter only in vacuum drying oven, dries down for 100 ℃ and promptly gets required silver-plated copper powder.
2. method according to claim 1 is characterized in that, the dilute acid soln that the described acid etching of step 3) is used is one or more compound of sulfuric acid, nitric acid or phosphoric acid.
3. method according to claim 1 is characterized in that, the palladium salt during the described catalytic liquid of step 5) is handled in the used catalytic liquid solution is one or more compound of Palladous chloride, dichloro diamino palladium, dichloro four ammonia palladiums.
4. method according to claim 1, it is characterized in that, used catalytic liquid solution was acidity or basic solution during described step 5) catalytic liquid was handled, and wherein the acid in the acidic solution is one or more compound in lactic acid, acetic acid, oxysuccinic acid, citric acid, hydrochloric acid or the boric acid; Basic solution is an ammonia soln; The concentration of acid or ammoniacal liquor is 12～30g/L in the catalytic liquid.
5. method according to claim 1 is characterized in that, the concentration of contained Silver Nitrate is 25～50g/L in the step 7) silver nitrate solution.
6. method according to claim 1, it is characterized in that, contained complexing agent is one or more the mixture in Trisodium Citrate, sodium-acetate, Sodium.alpha.-hydroxypropionate, quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the ammoniacal liquor in the step 7) silver nitrate solution, and concentration is 60～130g/L.
7. method according to claim 1 is characterized in that, the pH value of step 7) silver nitrate solution is 10～14.
8. method according to claim 1 is characterized in that, the described stirring of step 7) is machinery, induction stirring and hyperacoustic one or both alr modes.
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| CN110369712A (en) * | 2019-08-29 | 2019-10-25 | 嘉兴学院 | A kind of preparation method for covering silver-bearing copper powder |
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| CN102475094B (en) * | 2010-11-25 | 2014-06-18 | 徐永红 | Nanometer silver-copper-zinc alloy bactericidal material |
| CN102002694B (en) * | 2010-12-14 | 2012-07-04 | 江西理工大学 | Method for preparing uniform silver conducting layer on surface of metal or nonmetal material |
| CN102560451B (en) * | 2012-02-22 | 2013-12-11 | 江苏大学 | Chemical nano-silver plating solution and preparation method thereof, and silver plating method for copper part |
| 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 |
| CN103084581B (en) * | 2013-01-08 | 2015-02-04 | 河南大学 | Preparation method for copper nanowire |
| CN103157421B (en) * | 2013-04-07 | 2016-02-17 | 株洲市兴民科技有限公司 | Improve ultrasonic wave at the method for replacement process action effect and device |
| KR20170102977A (en) * | 2015-01-09 | 2017-09-12 | 클락슨 유니버시티 | Coated copper foil and a method for producing the same |
| CN105855538B (en) * | 2016-04-08 | 2018-09-07 | 广东工业大学 | A kind of nanometer of silver-coated copper powder, preparation method and application |
| CN106925774B (en) * | 2017-03-16 | 2019-06-07 | 重庆云天化瀚恩新材料开发有限公司 | A kind of preparation method of silver-coated copper powder |
| CN110842190B (en) * | 2019-10-11 | 2021-10-15 | 云南大学 | Preparation method of silver-coated copper powder |
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Non-Patent Citations (2)
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| 梅冰.银-铜复合粉的制备及性能研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2008,(第3期),12-17页. * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110369712A (en) * | 2019-08-29 | 2019-10-25 | 嘉兴学院 | A kind of preparation method for covering silver-bearing copper powder |
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