CN106498457A - A kind of new cyanide-free copper electroplating technique - Google Patents
A kind of new cyanide-free copper electroplating technique Download PDFInfo
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- CN106498457A CN106498457A CN201611211406.XA CN201611211406A CN106498457A CN 106498457 A CN106498457 A CN 106498457A CN 201611211406 A CN201611211406 A CN 201611211406A CN 106498457 A CN106498457 A CN 106498457A
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- copper
- carboxyethyl
- carboxyethyl thiosuccinic
- plating
- thiosuccinic acid
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of copper-plating technique for having used Novel Ligands, part is carboxyethyl thiosuccinic acid root, and typical electroplate liquid formulation is：Copper sulphate 0.3mol/L, carboxyethyl thiosuccinic acid hydrogen dipotassium 1mol/L, plating solution composition are simple, and stable performance is insensitive to impurity, nontoxic, not phosphorous, nitrogen, safety and environmental protection, and on iron and steel, bottoming adhesion is good, and coating crystallizes fine uniform.
Description
Technical field
The present invention relates to field of electroplating, especially cyanideless electro-plating field.
Background technology
There is copper coating good ductility, electric conductivity, thermal conductivity and anti-carburizi ng and anti-nitriding performance, some metals to exist
It is easy to deposition on copper and adhesion is good, therefore copper coating can be used for the bottom of pre-plating layer or multi-layer plating.Copper is most widely used
One of coating.
The widely used copper-plating technique of electroplating industry has at present：
Hydrosulphate copper-plating technique：With copper sulphate, sulfuric acid and brightener as main component, coating light, but due to copper ion
In free state, strong displacement reaction can occur on the active metals such as iron and steel, kirsite, aluminium alloy, generate loose
Displacement layer and affect binding force of cladding material, it is impossible to Direct Electroplating.Highly acid plating solution also has stronger corrosivity to base material.
Cyanide copper plating technique：With cuprous cyanide, potassium cyanide or Cymag as main component, copper ion is with complex compound shape
Formula is present, and does not replace on iron and steel, kirsite, good with base material adhesion, is widely used in bottoming coating, adds light
The coating of light can also be plated out after agent.But as cyanide has severe toxicity, run into the cyaniding that acidic materials can discharge severe toxicity
Hydrogen, normal production development security incident.Find substitute, mainly find the non-cyanide plating of the part for substituting cyanide ion
The focus that process for copper is always studied in the industry.
Pyrophosphate copper plating and hydroxy ethylene diphosphonic acid（HEDP）Copper-plating technique：This is two kinds of more similar works
Skill, plating solution complex compound mainly with the complex compound or copper ion of copper ion and pyrophosphate and HEDP as main component, both
Because copper ion be in complex ion state, can on iron and steel Direct Electroplating, and plating solution pH be alkalescent, corrosion-free to base material,
There is wide application.But due to two kinds of parts all phosphorus containing high concentration, and more difficult removal during wastewater treatment, enter ring
Water body " eutrophication " is easily caused in border.
So people always search for the copper facing part of a kind of low toxicity, not nitrogenous, P elements developing safer environmental protection
Copper-plating technique.Especially more significant on the electroplating technology of development copper alloy.
The present invention exactly such a part and technique.
Content of the invention
Contain carboxyethyl thiosuccinic acid root, copper in the plating solution of cyanide-free copper electroplating technique of the present invention.
The molecular structural formula of carboxyethyl thiosuccinic acid root is as shown in figure 1, the carboxyethyl thiosuccinic acid root includes energy
Enough dissociate the series compound of carboxyethyl thiosuccinic acid root, be carboxyethyl thiosuccinic acid and its copper, potassium, sodium, lithium,
One or more in rubidium, caesium, calcium, magnesium, the salt of ammonium or acid salt, preferably carboxyethyl thiosuccinic acid hydrogen di-potassium.Plating solution
The content of middle carboxyethyl thiosuccinic acid root is 0.1-2mol/L.
In plating solution, the content of copper is 0.05-2mol/L, in the plating solution mainly with copper and carboxyethyl thiosuccinic acid root
Complex form exist, or with copper and carboxyethyl thiosuccinic acid root and hydrogen ion or hydroxide ion or hydrone
Mixed ligand complex form is present, and it is a kind of or many in following material to prepare the raw material containing copper used during plating solution
Kind：Copper simple substance, cupric oxide, Kocide SD, basic copper carbonate, copper sulphate, copper nitrate, copper chloride, cupric pyrophosphate, cupric pyrophosphate
The network of potassium, cupric phosphate and its acid salt, carboxyethyl thiosuccinic acid mantoquita and its acid salt, carboxyethyl thiosuccinic acid root and copper
Polymerisable compounds, preferably copper sulphate.
Copper-plating technique anode of the present invention is copper or graphite, and negative electrode is plating piece, and the cathode-current density for using is
0.01-5 amperes/square decimeter, more wide in range, in this current density range, high/low currents density region Deposit appearance is consistent.
Copper plating bath of the present invention place through long-time after still clear stable, in plating solution, the concentration of each component upper and lower 30% becomes
During change, the composition of coating and outward appearance are not changed substantially, and a small amount of addition of the usual impurities metal ion such as nickel, zinc, iron is not yet
The significantly change of plating solution performance can be caused, when on iron and steel as bottom, adhesion is good.
Carboxyethyl thiosuccinic acid root toxicity is very low, and raw material is easy to get, not phosphorous in molecule, nitrogen, will not cause water body
Eutrophication and pollute environment, in sewage disposal commonly use decomposing bacteria nonhazardous effect, it is easy to degrade.
Description of the drawings
Chemical structural formulas of the Fig. 1 for carboxyethyl thiosuccinic acid root.
Specific embodiment
Embodiment 1：
Plating solution mixed dissolution according to the following formulation：
Carboxyethyl thiosuccinic acid hydrogen dipotassium 1mol/L
Copper sulphate 0.3mol/L
Water surplus
An iron plate is taken, acetone soak oil removing is used, then with watery hydrochloric acid immersion activation, is cleaned and be followed by the negative pole of dc source,
With a fine copper plate as anode, it is connected on the positive pole of dc source, positive pole is collectively disposed in the plating solution for preparing above with negative pole,
Current density is controlled in 0.5A/dm2, copper facing was taken out after 10 minutes, clean, dried up.
Coating even compact, half light of surface, after bending, coating is without coming off.
Embodiment 2：
500ml deionized waters are put in container with a scale, add carboxyethyl thiosuccinic acid 300g, then slow under agitation
48 grams of addition basic copper carbonate, after being completely dissolved again under agitation slowly add NaOH, determine pH be equal to 8.5 when,
Stop adding, deionized water is added to 1000ml scales.
Bath temperature is controlled for 50 DEG C.
An iron plate is taken, alcohol-pickled oil removing is used, then with dilute sulfuric acid immersion activation, is cleaned the negative pole being followed by dc source
On, with graphite cake as anode, it is connected on the positive pole of dc source, positive pole is collectively disposed in the plating solution for preparing above with negative pole,
Current density is controlled in 1A/dm2, copper facing was taken out after 5 minutes, clean, dried up.
Coating even compact, half light of surface, after bending, coating is without coming off.
Claims (4)
1. a kind of non-cyanide copper electroplating liquid, is characterized in that in copper plating bath containing carboxyethyl thiosuccinic acid root and copper.
2. according to claim 1 carboxyethyl thiosuccinic acid root include dissociating carboxyethyl thiosuccinic acid root be
Row compound, is in carboxyethyl thiosuccinic acid and its copper, potassium, sodium, lithium, rubidium, caesium, calcium, magnesium, the salt of ammonium or acid salt
Plant or multiple, preferably carboxyethyl thiosuccinic acid hydrogen dipotassium, in plating solution, the content of carboxyethyl thiosuccinic acid root is 0.1-
2mol/L.
3. in copper plating bath, the content of copper is 0.05-2mol/L according to claim 1, in the plating solution mainly with copper and carboxylic
The complex form of ethylenebis dithiocarbamate succinic is present, or with copper and carboxyethyl thiosuccinic acid root and hydrogen ion or hydrogen-oxygen
The mixed complex form of radical ion or hydrone is present, and it is following material to prepare the raw material containing copper used during plating solution
In one or more：Copper simple substance, cupric oxide, Kocide SD, basic copper carbonate, copper sulphate, copper nitrate, copper chloride, burnt phosphorus
Sour copper, cupric pyrophosphate potassium, cupric phosphate and its acid salt, carboxyethyl thiosuccinic acid mantoquita and its thio fourth of acid salt, carboxyethyl
Two acid groups and the complex compound of copper, preferably copper sulphate.
4. the copper-plating technique of electrolytic copper plating solution according to claim 1, anode is copper or graphite, and negative electrode is plating piece, uses
Cathode-current density is 0.01-5 amperes/square decimeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611211406.XA CN106498457A (en) | 2016-12-24 | 2016-12-24 | A kind of new cyanide-free copper electroplating technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611211406.XA CN106498457A (en) | 2016-12-24 | 2016-12-24 | A kind of new cyanide-free copper electroplating technique |
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| CN106498457A true CN106498457A (en) | 2017-03-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611211406.XA Pending CN106498457A (en) | 2016-12-24 | 2016-12-24 | A kind of new cyanide-free copper electroplating technique |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242381A (en) * | 2011-06-29 | 2011-11-16 | 杭州阿玛尔科技有限公司 | Alkaline non-cyanide copper plating solution with main coordination agent of methylenediphosphonate |
| 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 |
| CN103806032A (en) * | 2012-11-08 | 2014-05-21 | 无锡新三洲特钢有限公司 | Cyanide-free one-step rapid copper plating process for steel wire surface |
| CN105596614A (en) * | 2016-01-22 | 2016-05-25 | 李先强 | Traditional Chinese medicine composition for treating adenoviral pneumonia |
-
2016
- 2016-12-24 CN CN201611211406.XA patent/CN106498457A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242381A (en) * | 2011-06-29 | 2011-11-16 | 杭州阿玛尔科技有限公司 | Alkaline non-cyanide copper plating solution with main coordination agent of methylenediphosphonate |
| CN103806032A (en) * | 2012-11-08 | 2014-05-21 | 无锡新三洲特钢有限公司 | Cyanide-free one-step rapid copper plating process for steel wire surface |
| 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 |
| CN105596614A (en) * | 2016-01-22 | 2016-05-25 | 李先强 | Traditional Chinese medicine composition for treating adenoviral pneumonia |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170315 |
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| WD01 | Invention patent application deemed withdrawn after publication |