CN1757798A - Propanetriol non-cyanide bright copper plating liquid - Google Patents
Propanetriol non-cyanide bright copper plating liquid Download PDFInfo
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- CN1757798A CN1757798A CN 200510044536 CN200510044536A CN1757798A CN 1757798 A CN1757798 A CN 1757798A CN 200510044536 CN200510044536 CN 200510044536 CN 200510044536 A CN200510044536 A CN 200510044536A CN 1757798 A CN1757798 A CN 1757798A
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Abstract
A brightening non-cyanogen copper-plating liquid is proportionally prepared from copper sulfate propanetriol, sodium hydroxide, decahydrated sodium sulfate and ammonium citrate through preparing the solution of propanetriol and sodium hydroxide, dissolving copper sulfate in it, dissolving others in it, and deluting.
Description
Technical field
The present invention relates to the cyanide-free copper electroplating field, relate in particular to a kind of Propanetriol non-cyanide bright copper plating field.
Background technology
In order to obtain the good coating of bonding force,, plated the difference of part and selected preplating in the Electroplating Production often according to the difference of plating.The normal cyanide electroplating that adopts in pre-plating process in the past, but because CN has severe toxicity, very big to electroplater's Health cost; The sewage, waste gas that discharges CN simultaneously is serious environment pollution also.State Economic and Trade Commission's 32 commands of assigning in 2002 clearly stipulate, contain cyanogen and electroplate and will be limited to 2003 and eliminate.Accelerate the research of cyanogenless electroplating technology, realize cleaner production, strengthen environmental protection is extremely urgent.
Because cyanide electroplating contains prussiate, toxicity is very big, contaminate environment, and sewage disposal expense height, and its current efficiency is lower, and the plating staff of China is devoted to the research of cyanide-free copper electroplating always in recent years, below is the introduction of domestic and international several cyanide-free copper electroplating technologies.
(1) vitriol copper facing
The vitriol acid copper plating bath is a main component with copper sulfate, sulfuric acid, owing to easily generating displacement layer on steel part, zinc casting, aluminum component, this kind plating bath cause bonding force not enough, this solution is dispersed bad in addition, and coating is coarse, brightless, so the application before the 1950's is less.After the sixties in 20th century, people have developed the vitriol copper plating additive.The coating that obtains has excellent light and leveling property, and coating is very soft; The current efficiency height (near 100%) of plating bath, sedimentation velocity is fast, and low price is suitable for Copper Foil, plastic component plating bottom.The acid copper plating solution of high density has good dispersive ability and covering power, is suitable for the through-holes of printed circuit boards plating.Because the internal stress of the copper layer that obtains is very low,, therefore can be used as electroforming even the very thick coating of plating also can not cause the distortion of workpiece from the sulfuric acid plating bath.But the shortcoming of this plating maximum is comparatively harsh to the requirement of brightening agent, and plating needs preplating cyanogen copper on steel part, zinc casting, aluminum component.
(2) pyrophosphate copper plating
Pyrophosphate copper plating liquid is main salt with cupric pyrophosphate, and potassium pyrophosphate is main complexing agent, and is equipped with other ancillary components, is a kind of nearly neutral solution, and zinc-impregnating layer on zine pressure casting, the aluminium or the chemical plating on the plastics are not had erosion.Bath stability is better, is easy to control, and the dispersive ability of plating bath and covering power are all better, and cathode efficiency is also very high, can be used for producing in enormous quantities, and the coating crystallization is careful, and corrosion stability is good.Shortcoming is that cost is higher, and directly copper facing of steel part needs preplating or preimpregnation to improve the bonding force of coating; The pyrophosphate salt facile hydrolysis becomes orthophosphoric acid salt in the electrolytic solution, and when the phosphoric acid salt accumulation volume reached 80～100g/L, the copper sedimentation velocity descended, and waste water is difficult for handling.
(3) fluoroborate copper facing
The fluoroborate copper plating bath is based on the simple ion plating bath of fluoroborate, and its maximum characteristics are that cathode current density is big, and coating deposition rate is fast, easily obtain thicker coating, therefore be usually used in electroforming, but shortcoming is a plating bath cost height, big to equipment corrosion, the wastewater treatment difficulty.
(4) quadrol copper facing
Quadrol copper facing is main complexing agent with quadrol, and the covering power of plating bath is good, and the coating crystallization is careful, and outward appearance is good, but nickel plating bonding force again is poor after the copper facing, and this kind technology is seldom used.
(5) HEDP copper facing
HEDP (1-Hydroxy Ethylidene-1,1-Diphosphonic Acid) has strong sequestering action to metal ion.The non-cyanide alkali plating bath is adopted in HEDP copper facing, contains cupric, HEDP, buffer reagent or stablizer, wetting agent etc. in the prescription, and this kind technology can be plated on iron-based, copper base and zinc-base body and be got the good thin brilliant coating of malleable bonding force.But because solution composition complexity, technology are restive, and waste liquid is difficult to handle, and limited its widespread use.
(6) monovalence copper copper facing
In organic phosphonate alkaline copper plating electrolytic solution, add the halide-ions addition of C l of significant quantity
-, Br
-, F
-Or its mixture, thereby in organic phosphonate cupric plating bath, realize the copper facing of monovalence copper.On zine pressure casting, obtain the good copper coating of bonding force, quality near or be equivalent to the copper substrate of cyanide copper type.
Cupprous coordination anion plating bath not only has good electrochemistry and electroplating integrated performance, and energy-conservation.But this to use strong reductant and low pH value cuprous plating solution maintenance difficulty as feature, do not meet need of industrial production.
(7) other copper facing
Except that above-mentioned each technology, it is the copper plating bath of main complexing agent that people have also studied with Seignette salt, nitrilotriacetic acid(NTA), citric acid etc., though the stability of each technology plating bath is all relatively good, also can obtain light, coating that bonding force is good, but the preparation of plating bath is more loaded down with trivial details, and plating solution maintenance is difficult, and the operator is had relatively high expectations, the plating bath cost is higher, is difficult to realize industrial production.
Summary of the invention
For the deficiency of all kinds of platings in the solution prior art or the limitation of plating bath, the invention discloses a kind of Propanetriol non-cyanide bright copper plating liquid.
The Propanetriol non-cyanide bright copper plating liquid that the present invention adopts is characterized in that, fills a prescription mainly by copper sulfate 15～30g/L, and glycerol 5～16mL/L, sodium hydroxide 15～40g/L, sal glauberi 100～200g/L, ammonium citrate 10～40g/L forms.
Hydroxylic moiety in the prescription in the glycerol is replaced by the cupric ion in the plating bath, forms the organic copper salt plating bath, has closely increased the cathodic polarization effect; The adding of ammonium citrate is played the effect of auxiliary complexing to the cupric ion in the plating bath, when stablizing plating bath, has strengthened the cathodic polarization effect greatly, has widened the current density range of negative electrode, and gained coating is uniform and delicate more also.
Institute comprises each components contents and is preferably: copper sulfate 15～20g/L, glycerol 8～12mL/L, sodium hydroxide 15～20g/L, sal glauberi 100～150g/L, ammonium citrate 15～30g/L.
Above-mentioned prescription bath stability is good, and the dispersive ability and the covering power of plating bath are fine, and the cathode current density wide ranges of plating can obtain bonding force good even, bright, careful coating.
The pH value of plating bath is 7～8; The cathode current density scope can reach 0.1～3.0A/dm
2, and, improve the cathode current density higher limit simultaneously along with the cathode current density scope can be further widened in the rising of temperature; Cathode efficiency is up to 95.62%; It is careful to obtain full light in 20 ℃～60 ℃ scopes, and hole is few, the bright copper plating layer that bonding force is good.
Compound method of the present invention: the glycerol and the sodium hydroxide that take by weighing aequum, 2/3rds wiring solution-formings by joining plating bath cumulative volume, the copper sulfate dissolving back of getting respective amount in the prescription adds above-mentioned solution, sal glauberi and ammonium citrate are dissolved the adding coating bath respectively, be diluted with water to cumulative volume, solution is transparent mazarine.
The pH value of above-mentioned plating bath is 7～8, if the too high sulfuric acid that adopts of the pH of plating bath is regulated, regulates if pH crosses the low sodium hydroxide that can adopt.To join plating bath be nearly neutral environment in institute, can not cause corrosion to the plating part, can improve the bonding force of coating simultaneously with the function of oil removing, less demanding to equipment and coating bath, and production cost is low.
In the electroplating process, cathode current density can be according to circumstances at 0.1～3.0A/dm
2Choose in the scope, temperature can be 10～60 ℃, and anode adopts the electrolysis copper coin, and yin, yang area ratio is 1: 2～5, adopts negative electrode to move or the pressurized air stirring.
That this copper plating bath has is nontoxic, pollution-free, composition simple, to equipment do not have that the burn into production cost is low, bath stability, cathode current density wide ranges, gained coating be evenly smooth, light is careful, cathode efficiency is up to 95%, liquid waste disposal is easy, can not cause advantages such as secondary pollution, promptly can be used as pre-plating layer and also can be used as the decorative coating use, is a kind of novel copper plating bath that meets cleaner production.
Description of drawings
Fig. 1 is the influence of cathode current density to thickness of coating.
Fig. 2 is the influence of cathode current density to porosity.
Fig. 3 is the influence of temperature to thickness of coating.
Fig. 4 is the influence of temperature to porosity.
Embodiment
| Copper sulfate (g/L) | Glycerol (mL/L) | Sodium hydroxide (g/L) | Sal glauberi (g/L) | Ammonium citrate (g/L) | |
| | 15 | 5 | 20 | 100 | 30 |
| | 16 | 12 | 17 | 160 | 20 |
| | 17 | 16 | 22 | 110 | 40 |
| Embodiment 4 | 21 | 7 | 15 | 180 | 10 |
| Embodiment 5 | 23 | 14 | 24 | 150 | 35 |
| Embodiment 6 | 25 | 10 | 28 | 120 | 15 |
| Embodiment 7 | 28 | 9 | 30 | 130 | 25 |
| Embodiment 8 | 19 | 8 | 26 | 140 | 15 |
All take by weighing glycerol and sodium hydroxide according to above prescription, by 2/3rds wiring solution-formings of joining plating bath cumulative volume, the copper sulfate dissolving back of getting respective amount adds above-mentioned solution, and aqueous sodium persulfate and ammonium citrate dissolve the adding coating bath respectively, are diluted to cumulative volume.
The bath pH value of above-mentioned configuration is 7～8, at room temperature in 0.1～3.0A/dm
2The cathode current density scope in all can obtain the evenly good coating of bright careful bonding force.(wherein bonding force adopts the thermal shock method to measure) is as cathode current density D
K＜0.1A/dm
2The time, obtain extremely uneven coating.As cathode current density D
K＞3.0A/dm
2The time, coating burns.At 0.1～3.0A/dm
2In the cathode current density scope, identical electroplating time, with the increase of current density, thickness of coating increases gradually.Along with the increase of current density, current efficiency is rising trend, and the glossiness of coating is along with D
KIncrease, by bright to glow.Adopt above-mentioned prescription, when electroplating 3 minutes, cathode current density is seen Fig. 1 to the influence of thickness of coating, and cathode current density is seen Fig. 2 to the influence of porosity.
Above plating bath was electroplated 5 minutes respectively at room temperature, 30 ℃, 40 ℃, 50 ℃, 60 ℃, all can obtain the evenly good coating of bright careful bonding force.And along with the rising of bath temperature, the thickness of coating increases gradually, and the porosity of coating reduces gradually.Temperature is seen Fig. 3 to the influence of thickness of coating, and temperature is seen Fig. 4 to the influence of porosity.
Claims (4)
1. Propanetriol non-cyanide bright copper plating liquid is characterized in that prescription mainly by copper sulfate 15～30g/L, glycerol 5～16mL/L, and sodium hydroxide 15～40g/L, sal glauberi 100～200g/L, ammonium citrate 10～40g/L mixes.
2. Propanetriol non-cyanide bright copper plating liquid according to claim 1 is characterized in that, institute comprises each components contents and is preferably: copper sulfate 15～20g/L, glycerol 8～12mL/L, sodium hydroxide 15～20g/L, sal glauberi 100～150g/L, ammonium citrate 15～30g/L.
3. Propanetriol non-cyanide bright copper plating liquid as claimed in claim 1 or 2, it is characterized in that the plating technology parameter is respectively: cathode current density is 0.1～3.0A/dm
2, temperature is 10～60 ℃, the pH value is 7～8.
4. the compound method of Propanetriol non-cyanide bright copper plating liquid as claimed in claim 1 or 2, its step is as follows: the glycerol and the sodium hydroxide that take by weighing aequum, 2/3rds wiring solution-formings by joining plating bath cumulative volume, the copper sulfate dissolving back of getting respective amount adds above-mentioned solution, sal glauberi, ammonium citrate are dissolved adding respectively, be diluted with water to cumulative volume.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100445364A CN100362141C (en) | 2005-09-01 | 2005-09-01 | Propanetriol non-cyanide bright copper plating liquid |
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|---|---|---|---|
| CNB2005100445364A CN100362141C (en) | 2005-09-01 | 2005-09-01 | Propanetriol non-cyanide bright copper plating liquid |
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| CN1757798A true CN1757798A (en) | 2006-04-12 |
| CN100362141C CN100362141C (en) | 2008-01-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677116A (en) * | 2012-06-12 | 2012-09-19 | 山东建筑大学 | Method for dipulse preplating non-cyanide alkaline copper on ferro matrix |
| CN103668357A (en) * | 2013-12-19 | 2014-03-26 | 株洲永盛电池材料有限公司 | Alkaline cyanide-free high-speed copper plating solution |
| CN106835212A (en) * | 2017-03-29 | 2017-06-13 | 南京信息工程大学 | A kind of cyanideless electro-plating nanocrystalline copper electroplate liquid and its application method |
| CN114032588A (en) * | 2021-12-16 | 2022-02-11 | 东莞振顺五金制品有限公司 | Pre-plating solution and pre-plating process for cyanide-free alkaline copper plating, electroplating solution and electroplating process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW420729B (en) * | 1996-02-12 | 2001-02-01 | Gould Electronics Inc | A non-cyanide brass plating bath and a method of making metallic foil having a brass layer using the non-cyanide brass plating bath |
| JP3919474B2 (en) * | 2000-06-30 | 2007-05-23 | 株式会社荏原製作所 | Plating method and plating apparatus |
| JP3899313B2 (en) * | 2000-10-19 | 2007-03-28 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Electrodeposition method for copper bath and matte copper coating |
| JP2005023405A (en) * | 2003-07-02 | 2005-01-27 | Shinko Electric Ind Co Ltd | Copper electroplating solution and copper electroplating method |
-
2005
- 2005-09-01 CN CNB2005100445364A patent/CN100362141C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677116A (en) * | 2012-06-12 | 2012-09-19 | 山东建筑大学 | Method for dipulse preplating non-cyanide alkaline copper on ferro matrix |
| CN102677116B (en) * | 2012-06-12 | 2013-05-08 | 山东建筑大学 | Method for dipulse preplating non-cyanide alkaline copper on ferro matrix |
| CN103668357A (en) * | 2013-12-19 | 2014-03-26 | 株洲永盛电池材料有限公司 | Alkaline cyanide-free high-speed copper plating solution |
| CN103668357B (en) * | 2013-12-19 | 2016-08-17 | 湖南永盛新材料股份有限公司 | A kind of alkaline non-cyanide high-speed plating copper electrolyte |
| CN106835212A (en) * | 2017-03-29 | 2017-06-13 | 南京信息工程大学 | A kind of cyanideless electro-plating nanocrystalline copper electroplate liquid and its application method |
| CN106835212B (en) * | 2017-03-29 | 2019-07-16 | 南京信息工程大学 | A kind of cyanideless electro-plating nanocrystalline copper electroplate liquid and its application method |
| CN114032588A (en) * | 2021-12-16 | 2022-02-11 | 东莞振顺五金制品有限公司 | Pre-plating solution and pre-plating process for cyanide-free alkaline copper plating, electroplating solution and electroplating process |
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|---|---|
| CN100362141C (en) | 2008-01-16 |
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