CN105734622A - Cyanide-free copper plating solution and preparation method thereof - Google Patents
Cyanide-free copper plating solution and preparation method thereof Download PDFInfo
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- CN105734622A CN105734622A CN201610192048.6A CN201610192048A CN105734622A CN 105734622 A CN105734622 A CN 105734622A CN 201610192048 A CN201610192048 A CN 201610192048A CN 105734622 A CN105734622 A CN 105734622A
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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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Abstract
The invention provides a cyanide-free copper plating solution and a preparation method thereof. The cyanide-free copper plating solution comprises copper salt, main alkali, a copper salt coordination agent and a brightener, and is characterized in that the copper salt coordination agent comprises a main coordination agent and an auxiliary coordination agent, citric acid serves as the main coordination agent, and succinimide serves as the auxiliary coordination agent; and the brightener contains nicotinic acid, indole acitic acid, poly diaminourea and oxethyl-2-alkyne alcohol ether. The plating solution is stable, not prone to being muddied and high in impurity-resisting capacity; the bonding force of a plated copper layer and a matrix is good; the performance of the plating solution and the performance of the plated layer both can achieve the effect obtained by copper plating through cyanide; within the range that T ranges from 45 DEG C to 55 DEG C and the density ranges from 0.2 A/dm<2> to 3.5 A/dm<2>, the copper plated layer which is fine in crystallization, bright and soft can be obtained and can be sleeved with a nickel layer or a chromium layer or a nickel-chromium layer basically without polishing; the cathode current efficiency can reach 70% to 85%; and an electroplating method that sheets are inserted into pipes with phi being 10*100 mm and the pipes are parallel to anodes is adopted for testing, and the deep plating capacity can reach 100%.
Description
Technical field
The present invention relates to field of electroplating, particularly relate to a kind of non-cyanide alkali bright copper plating solution, its
Preparation method and electroplating technology thereof.
Background technology
Copper electroplating layer has good ductility, electric conductivity, heat conductivity, it is easy to polishing, and
With ferrum and other metal affinity is strong, adhesion is good, therefore copper coating can be as pre-plating layer or many
Layer plating bottom, save substantial amounts of nickel and other precious metal and be widely used in machinery,
The industrial circles such as electronics, Aero-Space, weapons, automobile, boats and ships.Due to current without cyanogen electricity
Copper facing technical matters is the most immature, and it is poor with iron-based body and other coat of metal adhesion to also exist,
The problems such as current density range is narrow, current efficiency is the highest, coating is the brightest.Therefore still suffer from present
The substantial amounts of cyanide copper technique using severe toxicity, causes environment, water source, soil
Severe contamination；And it is highly unwanted to health.To this end, country has promulgated regulation already, under
Make in addition to special most advanced and sophisticated defense technology, completely forbid and use cyanide plating to change into without cyanogen electricity
Depositing process.
At present, the Alkali CyanideFree Copper Electroplating Technology researched and developed mainly has: pyrophosphoric acid (salt) system,
Citric acid (salt) system, tartaric acid (salt) system, citric acid (salt) tartaric acid (salt) system,
Polyphosphate (HEDP) system, ethylenediamine system etc..The copper-plating technique of these alkalescence is all deposited
Having, plating solution impurity ability muddy, anti-unstable, easy is weak, on steel substrate, copper is the most replaced
The problems such as precipitation causes adhesion between copper plate and matrix poor.Most notably the performance of plating solution and
The performance of coating can't reach the effect using cyanide copper plating to be obtained.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of non-cyanide alkali light
Copper plating solution, its preparation method and electroplating technology thereof, its bath stability, be difficult to muddiness, anti-miscellaneous
Mass-energy power is strong, and the layers of copper plated is good with basal body binding force and the performance of plating solution and the property of coating
All can reach the effect using cyanide copper plating to be obtained.
The non-cyanide alkali bright copper plating solution of the present invention, including mantoquita, main alkali, mantoquita complexant
And brightener, described mantoquita complexant includes main complexant and auxiliary complexing agent, described brightener
Containing nicotinic acid, indoleacetic acid, poly-diaminourea and the one or in ethyoxyl-2-alkynol ether
More than Zhong.Preferably, described main complexant is citric acid, and described auxiliary complexing agent is succinyl
Imines.Described brightener contains nicotinic acid, indoleacetic acid, poly-diaminourea and ethyoxyl-2-alkynes
Alcohol ether.Described brightener is prepared by a kind of following method: step 1: with volume for 1000
In the container of milliliter, insert 25 grams of poly-diaminoureas, 15 grams of indoleacetic acids, 125 grams of ethoxies
Base-2-alkynol ether, adds 500～600 milliliters of distilled water or deionized water, stirs, dissolves；
Step 2: in the container that another volume is 250 milliliters, inserts 100～150 milliliters of distillations
Water, 5～10 grams of KOH；After potassium hydroxide has dissolved, add 2.5 grams of nicotinic acid while hot；Stir
Mix after being completely dissolved to nicotinic acid, join in the solution of above-mentioned steps 1；Then distilled water is filled into
To 1000 milliliters, stir.It is further preferred that described solution also includes boric acid.Institute
Stating boric acid to exist as a kind of reinforcing agent, after adding boric acid, the bright range of copper plate can be widened,
Brightness can improve.Further, described solution also includes sodium potassium tartrate tetrahydrate.Described tartaric acid
Potassium sodium exists as the stabilizer of a kind of plating solution, can maintain in solution copper ion and complexant it
Between balance.
Further, described solution also includes Cucurbituril.Described Cucurbituril is as a kind of plating solution
Anti-displacement dose of existence, is possible to prevent the phenomenon replacing copper to occur, makes copper coating produce with iron and steel parts
Raw good adhesion.
It is further preferred that described solution includes following component and content: the pH of described solution
Value is 9.0-11.Accordingly, the preparation of a kind of non-cyanide alkali bright copper plating solution of the present invention
Method, comprises the steps: that step a., in the container of 1000 milliliters, adds 300-600
The distilled water of milliliter or deionized water, be heated to 50 DEG C～60 DEG C；Add boric acid, treat boric acid
After having dissolved, then it is sequentially added into dissolving citric acid, succimide, four water Soluble tartar .s
Sodium；Copper sulphate pentahydrate, stirring and dissolving is added after having dissolved；Step b. in another container,
Add about 200-300 milliliter distilled water, be not required to heat and i.e. add potassium hydroxide, stirring and dissolving,
Join after cooling in the solution obtained by above-mentioned steps a；Step c. is then in step
In the solution obtained, it is sequentially added into Cucurbituril, brightener, moisturizing to 1000 milliliter, stirring
Uniformly；Step d. detects main salt and main alkali content value, with dilute sulfuric acid or dilute potassium hydroxide solution
Adjust pH value within normal range after can use.
A kind of non-cyanide alkali bright copper plating technique of the present invention, including pre-treatment, plating and after locate
Reason, described pre-treatment includes degreasing and rust removal and washing, and post processing includes drying, and described plating is adopted
With the above-mentioned a kind of non-cyanide alkali bright copper plating solution related to as plating solution.Preferably, plating the moon
Electrode current density is 0.2～3.5A/dm2.Galvanic anode is fine copper.
Advantages of the present invention: 1, bath stability, to be difficult to impurity ability muddy, anti-strong；2, plating
On layers of copper good with basal body binding force；3, the performance of plating solution and the performance of coating all can reach to adopt
The effect obtained with cyanide copper plating；4, at T=45 DEG C～55 DEG C, 0.2～3.5A/dm2
In the range of, all can obtain crystallizing careful, bright, soft copper coating, substantially need not polish,
Nickel, chromium or nicr layer can be overlapped the most again；5, cathode efficiency can reach 70～85%；
6, inserted sheet and galvanoplastic parallel with anode test, covering power in Φ 10 × 100 pipe is used
Up to 100%.
Detailed description of the invention
Below by the preferred non-cyanide alkali bright copper plating solution of the present invention, preparation method, work
Skill is described in detail, but is not limitation of the invention, for those skilled in the art
Some nonessential improvement and the adjustment made according to foregoing invention content, are also considered as at this
In bright protection domain.First the component of the non-cyanide alkali bright copper plating solution of the present invention is carried out in detail
Thin elaboration and selection.1, in the alkaline bright copper plating solution of the present invention, with cupric salt (sulfur
Acid copper), potassium hydroxide be main component.But copper sulfate is to be not directly added into potassium hydroxide solution
In, precipitation can be produced rapidly, therefore be then added to alkali after needing first mantoquita and complexant to be coordinated
In property liquid.Can have a lot with the complexant that copper carries out being coordinated, such as citric acid and salt, tartaric acid
And salt, ethylenediaminetetraacetic acid and salt, polyphosphate etc..Although they coordinations with copper
Ability all has certain ability, but because of its configurational energy after there is problems of joining in alkalies
Power unsatisfactory and easily by iron and steel parts chemical replacement copper, and then cause copper coating and matrix
The problems such as adhesion is poor, easy decortication, lose the copper plate Protection significance to workpiece.Therefore this
It is bright except have selected citric acid (under equal coordination ability, price is lower than its salt) as main complexant,
Have selected again succimide is auxiliary complexing agent.Succimide (is commonly called as butanimide),
In the plating of China's the seventies in last century is studied, once for the coordination of cyanide-free silver plating process
Agent；But so far and have not seen for the research of non-cyanide alkali bright copper plating and the report of production and specially
Profit is announced.The employing " citric acid-succimide " of the present invention is as master-auxiliary complexant.
Such compatibility so that mantoquita is more stable in potassium hydroxide solution, the copper plating bath prepared is for a long time
Production process in stable, do not produce muddiness and precipitation, and to Fe2+, Fe3+, Ni2+,
The pollution of the metal impurities such as Zn2+, Cr6+, Cr3+ also has tolerance well.2, the present invention
In, main alkali uses potassium hydroxide, shows through the experimentation of the present invention: with potassium hydroxide than using
Sodium hydroxide effect is more preferable, shows that coating stress is little, crystallizes than more careful, dividing of plating solution
Scattered property is the most superior.Such difference be possibly due to sodium, potassium atom peripheral electron configuration not
With (Na:3s1, K:4s1).Therefore in the system of the present invention, use no or little Na+ as far as possible.
3 it is known that in nickel plating solution, uses this material of H3BO3, its effect be because of
Cathode/Solution Interface, the pH value of solution easily raises, and can play buffering and make after adding H3BO3
With, stablize the pH value of nickel-plating liquid between 3.8-4.5.And at the non-cyanide alkali light of the present invention
In bright copper plating bath, used the potassium hydroxide of higher concentration, the body pH value of solution reach 9 with
On, belong to alkalescence, buffer agent need not be made with H3BO3.But the result of research is demonstrate,proved significantly
Real, after adding H3BO3, the bright range of copper plate can be widened, brightness can improve.H3BO3
Can be as the reinforcing agent of plating solution.Such as, when plating solution does not contains H3BO3, general bright current
Density range is only between 0.5～3.0A/dm2；And after adding 25～30g/LH3BO3, one
As bright current density range can be changed between 0.1～3.5A/dm2 (most preferably 0.2～
3.5A/dm2)；As its content 30g/L, the bright current density range of coating is not
Significantly change again；Therefore H3BO3 content to be defined as 25～30g/L optimal.4, in copper facing
During process is carried out, use pure copper anode plate.But when anodic current density is big, easily it is passivated,
Solution can produce copper powder；Anodic current density hour, may dissolve again very fast, cause solution
Middle copper ion concentration rises the fastest.Both of which is to obtaining preferable bright copper coating extremely
Unfavorable.
The present invention uses sodium potassium tartrate tetrahydrate can solve both of these case, can avoid anode blunt
Change phenomenon, the too fast dissolving of copper can be inhibited again, maintain copper ion in solution, complexant it
Between balance, it is ensured that plating solution steady in a long-term.Although 5 at alkaline potassium hydroxide solution
In-citric acid, auxiliary complexing agent-succimide that employs complexant, but at iron and steel parts
Upper direct copper plating, its adhesion is still slightly poorer than copper facing in cyanide solution.For this in the present invention
Non-cyanide alkali bright copper plating liquid in, also use one and can effectively block steel and put on ironware
The surfactant of recopper-Cucurbituril [is called for short (CB) n], and its molecular structural formula is as follows:
Cucurbituril belongs to supramolecular chemistry material.It all has well in highly acid or strongly basic medium
Stability, multiple carbonyls at its two ends are excellent cation binding sites, to various metals
Ion has extremely strong coordination ability.Just because of this coordination ability so that it is consumption is little
(0.01-0.05mg/L), in the case of, a very thin film layer is generated at plating piece Adsorption on Surface,
There is extremely strong binding ability with two side's metals of Cathode/Solution Interface, therefore make copper coating and steel
Ironworker's part produces adhesion well, and this bond strength is suitable with cyanide copper plating.Experiment table
Bright: surface is processed clean ironware, under the conditions of cold, put the light plating of the present invention into
In copper liquid 60 minutes, observing with the magnifier of 40 times after taking-up, ironware surface is pure the whitest, light
Bright, find no the displacement of copper, precipitation；Then, after being dried up, put in Laboratory air
Put 2 weeks, also do not find ironware have get rusty, metachromatism.And it is known that after workpiece is added
Enter coating bath to the time being energized only with several seconds, therefore not there will not be in body series and put
The phenomenon of recopper occurs.6, in above-mentioned basic bath, brightener need to be added and can obtain light
Bright copper plate.Have following molecular structure all can as the present invention for non-cyanide alkali light
Bright copper-plated brightener: the poly-diaminourea of nicotinic acid indoleacetic acid [molecular formula (C15H34O4N4)
N, herein, R=F, Cl, Br, I], and ethyoxyl-2-alkynol ether (molecular formula C8H14O4, knot
Structure formula is by carrying out detailed to the component of the non-cyanide alkali bright copper plating solution of the invention described above
Elaboration, principle analysis, experimental selection, obtain the preferred non-cyanide alkali bright copper plating of the present invention
Solution component: main salt is copper sulfate, main alkali is potassium hydroxide, and main complexant is citric acid, auxiliary
Helping complexant is succimide, and brightener is by nicotinic acid, indoleacetic acid, poly-diaminourea and second
Epoxide-2-alkynol ether forms.Addition reinforcing agent boric acid further, stabilizer sodium potassium tartrate tetrahydrate,
Anti-displacement dose of Cucurbituril.Yet further, component above is real respectively through HullCell
Test after testing with sulculus (0.5L, 1.0L, 2.0L, 5.0L), by test and adjustment,
Following component and content is included: the pH value of its solution is at 9.0-11 to currently preferred solution
Between.Wherein, Cucurbituril CB-n be formulated as follows (as a example by preparing 1000 milliliters):
One volume is in the container of 1000 milliliters, insert 500～600 milliliters distilled water (or go from
Sub-water), add 20～30 grams of KOH, after KOH has dissolved, weigh addition 1 gram while hot
Cucurbituril [(CB) n].Herein, n=1～3 is preferably.Treat that CB-n (i.e. (CB) n) dissolves
After Wan Quan, add distilled water (or deionized water) to 1000 milliliters, after stirring
Add, be used in copper plating bath.This liquid is 1.0mg/ml. brightener JC-Cu containing CB-n
It is formulated as follows (as a example by preparing 1000 milliliters): in container that volume is 1000 milliliters,
Insert 25 grams of poly-diaminoureas, 15 grams of indoleacetic acids, 125 grams of ethyoxyl-2-alkynol ether, add
Enter 500～600 milliliters of distilled water (or deionized water), stir, dissolve.At another volume
It is in the container of 250 milliliters, inserts 100～150 milliliters of distilled water, 5～10 grams of KOH；Treat
After KOH has dissolved, add 2.5 grams of nicotinic acid while hot；After stirring is completely dissolved to nicotinic acid, add
In a upper solution；Then fill into distilled water to 1000 milliliters, stir, light
The electroplating technology of agent JC-Cu. embodiment is as follows: workpiece → electrochemical deoiling → hot water wash → cold water
Wash → electrochemical degreasing → hot water wash → cold water washes → eliminates rust → wash → non-cyanide alkali light plating
Wherein, best cathodes electric current density is 0.2～3.5A/dm2 in copper → washing → drying.Plating sun
Pole uses fine copper.4) experiment effect of embodiment: the crystallization of copper coating that embodiment obtains is careful,
Bright, soft.Cathode efficiency is 75%, 77%, 80%.Substantially need not polish,
Overlap other operations follow-up such as nickel, chromium or nicr layer the most again；In using Φ 10 × 100 pipe
Inserted sheet and galvanoplastic parallel with anode test, covering power is up to 100%.Tried by broken outer property
Test tries, and the copper coating of embodiment does not falls off, flawless, the best with the adhesion of iron-based body.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention,
All equivalent variations made within the spirit and principles in the present invention, should be included in the present invention's
Within protection domain.
Claims (7)
1. a cyanide-free copper electroplating solution, including mantoquita, main alkali, mantoquita complexant and brightener, it is special
Levy and be: described mantoquita complexant includes main complexant and auxiliary complexing agent, described main complexant
For citric acid, described auxiliary complexing agent is succimide；Described brightener contains nicotinic acid, Yin
Diindyl acetic acid, poly-diaminourea and ethyoxyl-2-alkynol ether.
2. a kind of cyanide-free copper electroplating solution as claimed in claim 1, it is characterised in that: described brightener
Prepared by a kind of following method: step 1: in container that volume is 1300 milliliters,
Insert 40 grams of poly-diaminoureas, 20 grams of indoleacetic acids, 130 grams of ethyoxyl-2-alkynol ether, add
Enter 600～800 milliliters of distilled water or deionized water, stir, dissolve；Step 2: at another
Volume is in the container of 400 milliliters, inserts 200～300 milliliters of distilled water, 10～15 grams of KOH；
After potassium hydroxide has dissolved, add 3 grams of nicotinic acid while hot；After stirring is completely dissolved to nicotinic acid,
Join in the solution of above-mentioned steps 1；Then filling into distilled water to 1300 milliliters, stirring is all
Even.
3. a kind of cyanide-free copper electroplating solution as claimed in claim 2, it is characterised in that: described solution is also
Including boric acid.
4. a kind of cyanide-free copper electroplating solution as claimed in claim 3, it is characterised in that: described solution is also
Including sodium potassium tartrate tetrahydrate.
5. a kind of cyanide-free copper electroplating solution as claimed in claim 4, it is characterised in that: described solution is also
Including Cucurbituril.
6. a kind of cyanide-free copper electroplating solution as claimed in claim 5, it is characterised in that: described solution
PH value is 9.0-11.
7. the preparation method of a kind of cyanide-free copper electroplating solution described in claim 6, it is characterised in that bag
Include following steps: step a., in the container of 1300 milliliters, adds 400-700 milliliter
Distilled water or deionized water, be heated to 80 DEG C～90 DEG C；Add boric acid, treat that boric acid dissolves
After complete, then it is sequentially added into dissolving citric acid, succimide, Rochelle salt；
Copper sulphate pentahydrate, stirring and dissolving is added after having dissolved；Step b., in another container, adds
About 300-500 milliliter distilled water, is not required to heat and i.e. adds potassium hydroxide, stirring and dissolving, cooling
After join in above-mentioned steps a obtained by solution in；Then step c. obtains in step
In solution, it is sequentially added into Cucurbituril, brightener, moisturizing to 1300 milliliter, stir；
Step d. detects main salt and main alkali content value, adjusts pH with dilute sulfuric acid or dilute potassium hydroxide solution
Value within normal range after can use.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610192048.6A CN105734622A (en) | 2016-03-30 | 2016-03-30 | Cyanide-free copper plating solution and preparation method thereof |
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| CN201610192048.6A CN105734622A (en) | 2016-03-30 | 2016-03-30 | Cyanide-free copper plating solution and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011954A (en) * | 2016-07-25 | 2016-10-12 | 贵州大学 | Cyanide-free copper electro-plating solution, preparation method and using method thereof |
| CN110284163A (en) * | 2019-07-31 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN111501072A (en) * | 2020-05-09 | 2020-08-07 | 广东哈福科技有限公司 | Copper electroplating solution passivating agent and copper electroplating solution |
| CN112746293A (en) * | 2020-12-27 | 2021-05-04 | 盐城市科瑞达科技咨询服务有限公司 | Copper alkaline bright cleaning agent and preparation method thereof |
| WO2022174632A1 (en) * | 2021-02-22 | 2022-08-25 | 张志梁 | Cyanide-free alkaline copper plating electroplating solution for zinc alloy die casting member, preparation method therefor, and electroplating method |
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| CN103014788A (en) * | 2012-12-28 | 2013-04-03 | 武汉吉和昌化工科技有限公司 | Cyanide-free alkaline copper-plating brightener and preparation method for same |
| CN103046090A (en) * | 2012-12-28 | 2013-04-17 | 武汉吉和昌化工科技有限公司 | Additive capable of preventing copper replacement in cyanide-free alkaline coppering solution and preparation method thereof |
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| JPH05230687A (en) * | 1992-02-19 | 1993-09-07 | Ishihara Chem Co Ltd | Copper electroplating solution |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011954A (en) * | 2016-07-25 | 2016-10-12 | 贵州大学 | Cyanide-free copper electro-plating solution, preparation method and using method thereof |
| CN106011954B (en) * | 2016-07-25 | 2018-07-10 | 贵州大学 | Cyanideless electro-plating copper solution and preparation method thereof and application method |
| CN110284163A (en) * | 2019-07-31 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110284163B (en) * | 2019-07-31 | 2020-08-04 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN111501072A (en) * | 2020-05-09 | 2020-08-07 | 广东哈福科技有限公司 | Copper electroplating solution passivating agent and copper electroplating solution |
| CN111501072B (en) * | 2020-05-09 | 2021-01-05 | 广东哈福科技有限公司 | Copper electroplating solution passivating agent and copper electroplating solution |
| CN112746293A (en) * | 2020-12-27 | 2021-05-04 | 盐城市科瑞达科技咨询服务有限公司 | Copper alkaline bright cleaning agent and preparation method thereof |
| WO2022174632A1 (en) * | 2021-02-22 | 2022-08-25 | 张志梁 | Cyanide-free alkaline copper plating electroplating solution for zinc alloy die casting member, preparation method therefor, and electroplating method |
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Application publication date: 20160706 |