CN109868492A - A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof - Google Patents

A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof Download PDF

Info

Publication number
CN109868492A
CN109868492A CN201810482900.2A CN201810482900A CN109868492A CN 109868492 A CN109868492 A CN 109868492A CN 201810482900 A CN201810482900 A CN 201810482900A CN 109868492 A CN109868492 A CN 109868492A
Authority
CN
China
Prior art keywords
plating
cyanogen
electroplate liquid
copper electroplating
alkali copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810482900.2A
Other languages
Chinese (zh)
Inventor
徐友撑
郑崇统
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lin Hai Weixing Electroplating Co Ltd
Original Assignee
Lin Hai Weixing Electroplating Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lin Hai Weixing Electroplating Co Ltd filed Critical Lin Hai Weixing Electroplating Co Ltd
Priority to CN201810482900.2A priority Critical patent/CN109868492A/en
Publication of CN109868492A publication Critical patent/CN109868492A/en
Pending legal-status Critical Current

Links

Abstract

The present invention relates to field of electroplating, it is specifically related to a kind of no cyanogen alkali copper electroplating liquid and preparation method thereof.The electroplate liquid includes following components: cyanideless electro-plating complexing agent: 120-140g/L, cyanideless electro-plating mantoquita: 25-35g/L.The content of cyanogen root meets the standard of national clean manufacturing to pollute the environment small in draining when alkali copper electroplating liquid prepared by the present invention significantly reduces plating.And no cyanogen alkali copper electrolyte prepared by the present invention is used, obtains coating without foaming phenomena, binding force of cladding material is good, and stability is high.

Description

A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof
Technical field
The present invention relates to field of electroplating, it is specifically related to a kind of no cyanogen alkali copper electroplating liquid and preparation method thereof.
Background technique
Copper plating bath is divided into cyanide electroplating, cyanide-free copper electroplating two major classes.The advantages of cyanide electroplating electrolyte, is dispersibility and covers Lid ability is good, and electrolyte composition is simple, easy to maintain, and suitable for steel and iron parts and zinc, the bottoming coating of Al-alloy products etc., cyanide is made Complexing agent for complex compound electroplate liquid is the important source material in electroplating industry, is generallyd use by countries in the world.The disadvantage is that cyanogen Compound is severe poisonous chemicals, and making dead amount is only 5 milligrams, and can not be given treatment at all once absorbing.And cyanide is electroplated Cyanide content few then more than ten grams, up to more than 100 grams, the liquid measure of work nest in liquid lack then several decaliters, and up to several kilolitres are even Liters up to ten thousand, so that being polluted the environment in the draining of these plating containing cyanogen root.And cyanide transport, control are difficult, give up Cost of water treatment is high.In this regard, each state has all successively put into effect resolution and has defined discharge standard.Final goal is to cancel cyaniding Object plating, the technique for replacing this toxic with other technologies.Here it is start cyanideless electro-plating (Cyanide- occur Freeplating, non-cyanideplating) the reason of.
Cyanide-free copper electroplating is divided into acid copper-plating and alkaline copper plating.Acid copper-plating is mainly that thick copper layer, steel are plated on nickel or Copper substrate Ironware and zinc alloy piece all directly cannot carry out copper facing in acid copper electrolyte, generally require through alkaline copper plating in steel and iron parts and Zinc alloy surface carries out preplating and is convenient for subsequent acid copper-plating, nickel plating etc. to improve the binding force of coating and parent metal Technique.Pyrophosphate copper plating, sulfate electro-coppering, citric acid electro-coppering are widely used that in alkaline non-cyanide electro-coppering field Deng number of patent application are as follows: 201710963412.9, a kind of no cyanogen alkali copper electroplating composition is disclosed, without cyanogen alkali copper described in 1L The raw material for preparing of electroplating composition includes: bivalent cupric ion: 15~17g;Citric acid: 185~195g;Sodium potassium tartrate tetrahydrate: 50~ 60g;Potassium nitrate: 5~6.5g;1,2- 1,2-diaminocyclohexane tetraacetic acid: 0.5~1g;Wetting agent: 0.2~0.3g;Brightener: 1.2~ 1.6g;Leveling agent: 0.1~0.15g;Deionized water adds to 1L.Number of patent application are as follows: 201710738123.9, it discloses described Except hydrogen embrittlement agent includes following ingredient by weight: 0.1~1 part of polyethylene glycol and 0.1~10 part of rhodanate;The electroplate liquid is pressed Concentration includes following component: 30~45g/L cadmium sulfate, 40~60g/L potassium hydroxide, 20~50g/L citric acid, 20~180g/L Complexing agent and 0.2~11g/L remove hydrogen embrittlement agent.Above-mentioned patent application reduces the use of cyanide, reduces cyanide to environment Pollution, but its there is also some disadvantages, such as the problems such as plating solution is at high cost, and binding force is poor, and stability is bad.In steel and iron parts Direct copper plating can cannot obtain satisfactory copper plate due to the presence of displacement layers of copper.
Description is more currently on the market for cyanide-free alkaline copper plating process, and many additive suppliers have corresponding production Product.But realize that binding force of cladding material is good on kirsite substrate and stay in grade simultaneously high volume applications in production there is presently no.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of no cyanogen alkali copper electroplating liquid and its preparation processes, realize plating solution without cyanogen, low toxicity; Execute-in-place environment can be improved;And it realizes and crystallizes coating careful, that binding force is strong on kirsite substrate.
To achieve the above object, the present invention is realized by the following scheme:
A kind of no cyanogen alkali copper electroplating liquid, the electroplate liquid includes following components:
Cyanideless electro-plating complexing agent 120-140g/L
Cyanideless electro-plating mantoquita 25-35g/L.
The electroplate liquid includes following components:
Cyanideless electro-plating complexing agent 125-135g/L
Cyanideless electro-plating mantoquita 28-32g/L.
The complexing agent are as follows: polymerization potassium rhodanide ammonium, the mantoquita are as follows: polymerization cuprous sulfocyanide.
When plating, the current density for giving the electroplate liquid is 0.5-2A/dm2.The working ph values of the electroplate liquid are 11 ~12, the operating temperature of the electroplate liquid is 45~55 DEG C.
A method of preparing no cyanogen alkali copper electroplating liquid, comprising the following steps:
(1) it takes the water of total volume 50%, is added cyanideless electro-plating complexing agent, heating is stirred to being completely dissolved;
(2) paste is tuned into water dissolution cyanideless electro-plating mantoquita, be added in step (1), it is stirring while adding to being completely dissolved;
(3) plus water is settled to solution and reaches total volume;
(4) activated carbon adsorption, filtering is added;
(5) normal temperature is heated up to get electroplate liquid.
Beneficial effects of the present invention:
(1) when alkali copper electroplating liquid prepared by the present invention significantly reduces plating in draining cyanogen root content, thus to ring Border pollution is small, meets the standard of national clean manufacturing.
(2) it is electroplated using no cyanogen alkali plating solution prepared by the present invention, obtains coating without foaming phenomena, binding force of cladding material is good, surely Qualitative height.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained under that premise of not paying creative labor belongs to the model that the present invention protects It encloses.
A kind of no cyanogen alkali copper electroplating liquid, the electroplate liquid includes following components:
Cyanideless electro-plating complexing agent 120-140g/L
Cyanideless electro-plating mantoquita 25-35g/L.
The electroplate liquid includes following components:
Cyanideless electro-plating complexing agent 125-135g/L
Cyanideless electro-plating mantoquita 28-32g/L.
The above-mentioned specific substance chemical name of complexing agent is known as polymerizeing potassium rhodanide ammonium, and general formula is (NH2K)mC2nN2n+1SOnHn+3; Wherein, 1≤n≤50,1≤m≤50.Mantoquita: thiocyanic acid class organic copper salt is polymerization cuprous sulfocyanide, general formula CumC2nN2n+ 1SOnHn+3;Wherein, 1≤n≤50,1≤m≤50.Wherein, 1≤n≤50,1≤m≤50.Above-mentioned polymerization potassium rhodanide ammonium, polymerization Cuprous sulfocyanide is obtained in market purchasing.
Using polymerization potassium rhodanide ammonium and it polymerize main component of the cuprous sulfocyanide as electroplate liquid, because of thiocyanate polarity By force, and it is polymer form, easily with formation hydrogen bond, improves the stability of coating.The two synergistic effect simultaneously, further improves The binding force of coating, while can obtain uniformly, careful, the non-cyanide plating layer of bubble-free phenomenon.
When plating, the current density for giving the electroplate liquid is 0.5-2A/dm2.Preferably, the electric current of the electroplate liquid is close Degree is 1A/dm2.The working ph values of the electroplate liquid be 11~12, it is preferred that the working ph values of the electroplate liquid be 11.2~ 12.The operating temperature of the electroplate liquid is 45~55 DEG C, and the operating temperature of the preferred electroplate liquid is 48~53 DEG C.
The present invention also provides a kind of methods for preparing no cyanogen alkali copper electroplating liquid, comprising the following steps:
(1) it takes the water of total volume 50%, is added cyanideless electro-plating complexing agent, heating is stirred to being completely dissolved;
(2) paste is tuned into water dissolution cyanideless electro-plating mantoquita, be added in step (1), it is stirring while adding to being completely dissolved;
(3) plus water is settled to solution and reaches total volume;
(4) activated carbon adsorption, filtering is added;
(5) normal temperature is heated up to get electroplate liquid.
Embodiment 1
Cyanideless electro-plating liquid of the invention includes following substance:
It polymerize potassium rhodanide ammonium 125g/L
It polymerize cuprous sulfocyanide 28g/L
Remaining is water
Electrolyte preparation: (1) it weighs 125g polymerization potassium rhodanide ammonium and 500ml water is added, heating, stirring is to being completely dissolved; (2) paste is tuned into a small amount of water by polymerised sulphur cyanogen is cuprous, be added in step (1), it is stirring while adding to being completely dissolved;(3) add water It is 1L to liquor capacity;(4) activated carbon adsorption, filtering is added;(5) 48 DEG C are heated up to;
When plating, the current density for giving the electroplate liquid is 1A/dm2;The working ph values of the electroplate liquid are 11.2, institute The operating temperature for stating electroplate liquid is 48 DEG C;Anodic current density is greater than 1ASD;Anode material is cathode copper;Coating bath is hardness PVC; It is heated using steam.
Embodiment 2
Cyanideless electro-plating liquid of the invention includes following substance:
It polymerize potassium rhodanide ammonium 135g/L
It polymerize cuprous sulfocyanide 32g/L
Remaining is water
Electrolyte preparation: (1) it weighs 135g polymerization potassium rhodanide ammonium and 500ml water is added, heating, stirring is to being completely dissolved; (2) paste is tuned into a small amount of water by 32g polymerised sulphur cyanogen is cuprous, be added in step (1), it is stirring while adding to being completely dissolved;(3) add Water to liquor capacity is 1L;(4) activated carbon adsorption, filtering is added;(5) 52 DEG C are heated up to;
When plating, the current density for giving the electroplate liquid is 1A/dm2;The working ph values of the electroplate liquid are 11.5, institute The operating temperature for stating electroplate liquid is 52 DEG C;Anodic current density is greater than 1ASD;Anode material is cathode copper;Coating bath is hardness PVC; It is heated using steam.
Embodiment 3
Cyanideless electro-plating liquid of the invention includes following substance:
It polymerize potassium rhodanide ammonium 120g/L
It polymerize cuprous sulfocyanide 25g/L
Remaining is water
Electrolyte preparation: (1) it weighs 120g polymerization potassium rhodanide ammonium and 500ml water is added, heating, stirring is to being completely dissolved; (2) paste is tuned into a small amount of water by 25g polymerised sulphur cyanogen is cuprous, be added in step (1), it is stirring while adding to being completely dissolved;(3) add Water to liquor capacity is 1L;(4) activated carbon adsorption, filtering is added;(5) 55 DEG C are heated up to;
When plating, the current density for giving the electroplate liquid is 0.5A/dm2;The working ph values of the electroplate liquid are 12, institute The operating temperature for stating electroplate liquid is 55 DEG C;Anodic current density is greater than 1ASD;Anode material is cathode copper;Coating bath is hardness PVC; It is heated using steam.
Embodiment 4
Cyanideless electro-plating liquid of the invention includes following substance:
It polymerize potassium rhodanide ammonium 140g/L
It polymerize cuprous sulfocyanide 35g/L
Remaining is water
Electrolyte preparation: (1) it weighs 140g polymerization potassium rhodanide ammonium and 500ml water is added, heating, stirring is to being completely dissolved; (2) paste is tuned into a small amount of water by 35g polymerised sulphur cyanogen is cuprous, be added in step (1), it is stirring while adding to being completely dissolved;(3) add Water to liquor capacity is 1L;(4) activated carbon adsorption, filtering is added;(5) 52 DEG C are heated up to;
When plating, the current density for giving the electroplate liquid is 1.8A/dm2;The working ph values of the electroplate liquid are 11.0, The operating temperature of the electroplate liquid is 52 DEG C;Anodic current density is greater than 1ASD;Anode material is cathode copper;Coating bath is hardness PVC;It is heated using steam.
Comparative example 1
The specific embodiment of comparative example 1 with embodiment 1, the difference is that: the no cyanogen alkali copper electroplating liquid does not wrap Include polymerization potassium rhodanide ammonium.
Comparative example 2
Comparative example 2 prepares electroplate liquid using the method described in embodiment 1 of Patent No. 201710738123.9.
Performance test:
Above-described embodiment 1-4, comparative example 1-2 are tested for the property by the following method, see Table 1 for details for test result.
1. hull trough test:
The addition plating solution 250ml in the slot of the Hull 267ml, cathode long 100mm, width 66mm, thickness 0.3mm standard brass piece, Plating solution, anode width 63mm, long 65mm cathode copper are put into after oil removing activates.Plating conditions: 48 DEG C of temperature, electric current 1A, time 5min, stirring.Clear water cleaning is used after plating, passivated cleaning pure water cleaning is observed after electric hot-air dries up again.
2. thickness of coating is tested:
Kirsite pull head product plates after pre-treatment oil removing activation without cyanogen alkali copper.Without cyanogen alkali copper electrolyte 50 DEG C, electric current it is close Spend 1A/DM2 under the conditions of, be electroplated 15min, 7.824 microns of thickness of coating.
3. quality of coating:
Plating is without cyanogen alkali copper after pre-treatment oil removing activation for kirsite pull head product, and process conditions: temperature 50 C, electric current are close 1A/dm2, time 15min, baking of being painted after subsequent electricity coke-plated copper, sour copper, copper-nickel alloy tin again, baking condition: 120 DEG C, 90min.
4. binding force
This experiment tests binding force of cladding material, high-temperature baking condition: 120 DEG C, 90min using high-temperature baking.If coating is not It is then qualified for foaming phenomena occur, is otherwise unqualified.
1 the performance test results of table
By the above results as can be seen that being electroplated using electroplate liquid described in embodiment when the present invention, coating combines Power is good, and coating crystallization is careful, uniformly, and bubble-free phenomenon.
It should be understood that above-mentioned specific embodiment of the invention is used only for exemplary illustration or explains of the invention Principle, but not to limit the present invention.Therefore, that is done without departing from the spirit and scope of the present invention is any Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.In addition, appended claims purport of the present invention Covering the whole variations fallen into attached claim scope and boundary or this range and the equivalent form on boundary and is repairing Change example.

Claims (7)

1. a kind of no cyanogen alkali copper electroplating liquid, it is characterised in that: the electroplate liquid includes following components:
Cyanideless electro-plating complexing agent 120-140g/L
Cyanideless electro-plating mantoquita 25-35g/L.
2. no cyanogen alkali copper electroplating liquid according to claim 1, it is characterised in that: the electroplate liquid includes following components:
Cyanideless electro-plating complexing agent 125-135g/L
Cyanideless electro-plating mantoquita 28-32g/L.
3. no cyanogen alkali copper electroplating liquid according to claim 1 or 2, it is characterised in that: the complexing agent are as follows: polymerised sulphur cyanogen Sour potassium ammonium, the mantoquita are as follows: polymerization cuprous sulfocyanide.
4. no cyanogen alkali copper electroplating liquid according to claim 1 or 2, it is characterised in that: when plating, give the electroplate liquid Current density is 0.5-2A/dm2
5. no cyanogen alkali copper electroplating liquid according to claim 1 or 2, it is characterised in that: the working ph values of the electroplate liquid are 11~12.
6. -3 is any described without cyanogen alkali copper electroplating liquid according to claim 1, it is characterised in that: the work temperature of the electroplate liquid Degree is 45~55 DEG C.
7. a kind of method for preparing electroplate liquid as claimed in claim 3, it is characterised in that: the following steps are included:
(1) it takes the water of total volume 50%, is added cyanideless electro-plating complexing agent, heating is stirred to being completely dissolved;
(2) paste is tuned into water dissolution cyanideless electro-plating mantoquita, be added in step (1), it is stirring while adding to being completely dissolved;
(3) plus water is settled to solution and reaches total volume;
(4) activated carbon adsorption, filtering is added;
(5) normal temperature is heated up to get electroplate liquid.
CN201810482900.2A 2018-05-18 2018-05-18 A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof Pending CN109868492A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810482900.2A CN109868492A (en) 2018-05-18 2018-05-18 A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810482900.2A CN109868492A (en) 2018-05-18 2018-05-18 A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109868492A true CN109868492A (en) 2019-06-11

Family

ID=66915426

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810482900.2A Pending CN109868492A (en) 2018-05-18 2018-05-18 A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109868492A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113005491A (en) * 2021-02-26 2021-06-22 深圳市新富华表面技术有限公司 Cyanide-free alkali copper electroplating process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014787A (en) * 2012-12-28 2013-04-03 广东达志环保科技股份有限公司 Copper-electroplating solution and electroplating process thereof
CN105274589A (en) * 2014-05-28 2016-01-27 无锡永发电镀有限公司 Alkaline cyanogen-free copper plating electroplating liquid and electroplating method thereof
CN105543909A (en) * 2016-03-09 2016-05-04 重庆立道表面技术有限公司 Cyanide-free alkaline copper electroplating solution and electroplating technology
CN107604392A (en) * 2017-09-29 2018-01-19 佛山市春暖花开科技有限公司 A kind of electroplate liquid of copper
CN107604393A (en) * 2017-10-17 2018-01-19 广州睿邦新材料科技有限公司 One kind is without cyanogen alkali copper electroplating composition and preparation method thereof
CN107829116A (en) * 2017-12-14 2018-03-23 广州三孚新材料科技股份有限公司 Cyanide-free alkaline copper plating electroplate liquid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014787A (en) * 2012-12-28 2013-04-03 广东达志环保科技股份有限公司 Copper-electroplating solution and electroplating process thereof
CN105274589A (en) * 2014-05-28 2016-01-27 无锡永发电镀有限公司 Alkaline cyanogen-free copper plating electroplating liquid and electroplating method thereof
CN105543909A (en) * 2016-03-09 2016-05-04 重庆立道表面技术有限公司 Cyanide-free alkaline copper electroplating solution and electroplating technology
CN107604392A (en) * 2017-09-29 2018-01-19 佛山市春暖花开科技有限公司 A kind of electroplate liquid of copper
CN107604393A (en) * 2017-10-17 2018-01-19 广州睿邦新材料科技有限公司 One kind is without cyanogen alkali copper electroplating composition and preparation method thereof
CN107829116A (en) * 2017-12-14 2018-03-23 广州三孚新材料科技股份有限公司 Cyanide-free alkaline copper plating electroplate liquid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113005491A (en) * 2021-02-26 2021-06-22 深圳市新富华表面技术有限公司 Cyanide-free alkali copper electroplating process

Similar Documents

Publication Publication Date Title
CN101532153B (en) Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process
CN101935836B (en) Surface treatment process of reddened copper foil for high-grade FR-4 copper-clad plate
CN107604393A (en) One kind is without cyanogen alkali copper electroplating composition and preparation method thereof
CN101760768A (en) Electroplating solution for cyanide-free silver plating and cyanide-free silver plating method
EP2283170A1 (en) Pd and pd-ni electrolyte baths
CN102304734A (en) Alkali system electroplating bright zinc-nickel alloy process
CN102171386B (en) Zinc alloy electroplating baths and processes
Du et al. Effect of coordinated water of hexahydrate on nickel platings from choline–urea ionic liquid
CN103806053A (en) Dual-pulse gold plating process
CN105780070B (en) A kind of Electrodeposition of Zn-ni Alloy In Alkaline Bath technique and its series additive
CN107119292A (en) A kind of nickel plating solution and the method for nickel plating
CN109868492A (en) A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof
CN112899738A (en) Steel matrix direct cyanide-free copper plating electroplating solution under strong acid condition and preparation method thereof
CN105018978A (en) Surface processing technology improving high-temperature stripping-resisting performance of electrolytic copper foil
CN105369305A (en) A copper-nickel alloy electroplating solution and an electroplating method thereof
CN103510133A (en) Carrier brightening agent as well as preparation method and application thereof
CN103388164A (en) Non-cyanide alkaline copper electroplating process and formula
CN103806056A (en) Chromium electroplating process for stainless steel surface
CN105442000A (en) Alkaline zinc-iron alloy electroplate liquid, preparation method and electroplating process
CN102690975B (en) Ternary tin-zinc alloy and electroplating method thereof
CN108203837A (en) A kind of no cyamelide copper and tin electroplate liquid and its preparation method
CN105112952A (en) Electroplating solution for non-cyanide silver electrodeposition, and electroplating method
CN103173817A (en) Environmental-friendly electrosilvering solution
TWI670398B (en) Nickel electroplating compositions with cationic polymers and methods of electroplating nickel
CN105002535A (en) Copper alloy electroplating solution and electroplating method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190611