CN105543908A - Solution and method for cyanide-free alkaline bright barrel copper plating - Google Patents
Solution and method for cyanide-free alkaline bright barrel copper plating Download PDFInfo
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- CN105543908A CN105543908A CN201610111574.5A CN201610111574A CN105543908A CN 105543908 A CN105543908 A CN 105543908A CN 201610111574 A CN201610111574 A CN 201610111574A CN 105543908 A CN105543908 A CN 105543908A
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/16—Apparatus for electrolytic coating of small objects in bulk
- C25D17/18—Apparatus for electrolytic coating of small objects in bulk having closed containers
- C25D17/20—Horizontal barrels
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonics, vibrations
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Abstract
The invention discloses a solution and a method for cyanide-free alkaline bright barrel copper plating. The solution comprises a No.1 BH-582 plating bath solution, 300 ml/L of a No.2 BH-582 plating bath solution, 10 ml/L of an additive and a pH value regulator, wherein the addition amount of the No.1 BH-582 plating bath solutions is calculated in such a manner that the content of copper ions in a final system is 5-7 g/L after the No.1 BH-582 plating bath solution and the No.2 BH-582 plating bath solution are matched, and the usage amount of the pH value regulators is based on the condition that the pH of the final system is kept between 9 and 11; the additive comprises a brightener, a bath change agent and a wetting agent in the volume ratio being 1:(1-3):1. The method for cyanide-free alkaline bright barrel copper plating adopts the solution for barrel copper plating and comprises steps as follows: pretreatment of an iron-based blank, activation, water washing and then cyanide-free alkaline bright barrel copper plating. On the basis that the binding force between plating and a matrix is guaranteed, the solution and the method can replace a cyanide system for pre-plating, and environment-friendly and clean production is realized.
Description
Technical field
The invention belongs to electrochemical surface scientific and engineering field, particularly a kind of non-cyanide alkali light rolls copper-plated solution and method.
Background technology
Cyanide copper plating is for a long time as in barrel plating process for copper, but prussiate toxicity is large, and causing serious threat to operative employee's human and environment, cause prussiate barrel plating copper and cleaner production to be runed counter to, is therefore the direction of Future Development without cyanogen barrel plating copper.Non-cyanide alkali barrel plating copper is the product of national cleaner production demand for development, eliminate cyanide electroplating to a great extent to the harm of operator and environment, many researchers have paid many painstaking effort in the exploration and popularization of cyanogenless electroplating technology, have also made significant headway.
At present, compared with cyaniding barrel plating copper, also there is following problem without cyanogen barrel plating copper in tradition: (1) luminance brightness comparatively adds additive prussiate and rolls copper-plated difference; (2) also there is certain distance in bonding force, and especially the bonding force bad phenomenon such as coating and matrix decortication, easily appears in barrel nickel plating again after thin pieces barrel plating copper; (3) some reported in literature, need during plating charged enter groove, make troubles to operation.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, provides a kind of non-cyanide alkali light to roll copper-plated solution.
Another object of the present invention is to provide a kind of non-cyanide alkali light to roll copper coating.
Object of the present invention is achieved through the following technical solutions: a kind of non-cyanide alkali light rolls copper-plated solution, comprises following composition:
No. 1, BH-582 open cylinder agent, No. 2, BH-582 open cylinder agent, additive and pH value regulator;
The concentration that No. 2, BH-582 open cylinder agent is 300mL/L, the content that the addition that No. 1, BH-582 open cylinder agent rolls cupric ion in the final system of copper-plated solution with described non-cyanide alkali light after arranging in pairs or groups by itself and No. 2, BH-582 open cylinder agent is that 5 ~ 7g/L calculates, the concentration of additive is 10ml/L, and the consumption of pH value regulator maintains pH9 ~ 11 with final system and is as the criterion;
Additive by concentration be the brightening agent of 1 ~ 10g/L, wetting agent 1:(1 ~ 3 by volume of concentration to be walk agent and the concentration of 0.1 ~ 20g/L be 10 ~ 50g/L): 1 forms.
Described brightening agent is preferably 1, 4-butynediol (BOZ), pyridinium hydroxy propyl sulfobetaine (PPS-OH), propiolic alcohol propoxylated compounds (PAP), propiolic alcohol (PA), propane sulfonic acid pyridinium salt (PPS), propiolic alcohol ethoxy compound (PME), N, N-diethyl propargylamine (DEP), N, N-PABS (PABS), N, N-diethyl propargylamine propane sulfonic acid inner salt (DEPS), butynediol ethoxy compound (BEO), butynediol propoxylated compounds (BMP), one in proyl sodium sulfonate (PS) and sodium allyl sulfonate (ALS) or at least two kinds.
The described agent that walks is preferably one in saltpetre, SODIUMNITRATE, hydrogen peroxide, L-glutamic acid, Sodium Thiocyanate 99, tin anhydride, tellurium dioxide, gelatin and peptone or at least two kinds.
Described wetting agent is polyoxyethylene glycol, and being preferably molecular weight is the polyoxyethylene glycol of 3000 ~ 6000; Be more preferably in polyethylene glycol 6000 (PEG6000) and Macrogol 3000 (PEG3000) one or both.
Described pH value regulator is one or both in bronsted lowry acids and bases bronsted lowry.
Described acid is preferably at least one in nitric acid, sulfuric acid and hydrochloric acid.
Described alkali is preferably at least one in sodium hydroxide, potassium hydroxide and ammoniacal liquor.
A kind of non-cyanide alkali light rolls copper coating, uses above-mentioned non-cyanide alkali light to roll copper-plated solution and carries out barrel plating copper.
Described non-cyanide alkali light rolls copper coating, carries out non-cyanide alkali light barrel plating copper after comprising the steps: the pre-treatment of iron-based blank, activation and washing.
Described non-cyanide alkali light rolls copper coating, specifically comprises the steps:
(1) pass-through mode 1. or mode 2. carry out electrochemical deoiling:
1. iron-based blank is placed in the without phosphorus degreasing powder solution of BH-13, carries out the process of straight reel electrochemical deoiling in 55 ~ 65 DEG C; In degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 40 ~ 60g/L; Oil removing time 40-60min;
2. iron-based blank is placed in the without phosphorus degreasing powder solution of BH-13, carries out the process of ultrasound wave barrel electrochemical deoiling in 25 ~ 35 DEG C; In degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 20 ~ 40g/L, oil removing time 10 ~ 20mim;
(2) wash: wash with water step (1) pass-through mode 1. or mode 2. carry out the iron-based blank that electrochemical deoiling obtains, remove surface residual except oil solution;
(3) activate:
1) the iron-based blank washed when step (2) is 1. carry out electrochemical deoiling by step (1) mode, activation step is: the clean iron-based blank of washing is soaked 5 ~ 10min in concentration is the sulphuric acid soln of volume percent 10% or the hydrochloric acid soln of volume percent 20%, obtains the iron-based blank activated;
2) the iron-based blank washed when step (2) is 2. carry out electrochemical deoiling by step (1) mode, activation step is: the clean iron-based blank of washing is soaked 1 ~ 2min in concentration is the sulphuric acid soln of volume percent 1% or the hydrochloric acid soln of volume percent 5%, obtains the iron-based blank activated;
(4) wash: the iron-based blank washing the activation that step (3) obtains with water, remove the acid solution of surface residual;
(5) neutralize: the sodium hydroxide solution of functional quality per-cent 1% carries out neutralizing treatment to the iron-based blank that step (4) obtains, prevent the iron-based blank activated from getting rusty, change to traditional cylinder;
(6) wash: the iron-based blank washing the activation that step (5) obtains with water, remove the alkaline solution of surface residual;
(7) activate: the iron-based blank cleaned up that step (6) obtains soaks 10s in the sulfuric acid solution liquid of volume percent 0.1%, obtain the iron-based blank activated;
(8) wash: the iron-based blank washing the activation that step (7) obtains with water, remove the acid solution of surface residual;
(9) non-cyanide alkali light barrel plating copper: more than one adopting in solvable anaerobic electrolytic copper or insoluble stainless steel, DSA coated anode are anode, the iron-based blank cleaned up in step (8) is negative electrode workpiece to be plated, be placed in above-mentioned non-cyanide alkali light and roll copper-plated solution, carry out barrel plating; When anode is soluble, in electroplating process, in plating solution, supplement No. 1, BH-582 open cylinder agent, make the concentration of cupric ion in cyanide-free plating bath keep initial value, and regulate the pH value of plating solution to be 9 ~ 11; Obtain the iron-base part after barrel plating.
Described non-cyanide alkali light rolls copper coating, also comprises conventional subsequent processing steps, by the iron-base part washing after the barrel plating that step (9) obtains, removes remaining plating solution; Carry out follow-up plating or electroless plating again.
The structure of the ultrasound wave barrel described in step (1) is as follows: comprise treatment trough, cylinder, web member, transmission rig, motor, ultrasonic wave plate and ultrasonic generator, described cylinder hangs in treatment trough by web member, described cylinder is connected with motor by transmission rig, described ultrasonic wave plate is installed on the sidewall of cylinder, and described ultrasonic wave plate is connected with ultrasonic generator.
Preferably, described cylinder cross section be regular hexagon.
Preferably, the quantity of described ultrasonic wave plate is 1 ~ 4.
Preferably, the quantity of described ultrasonic wave plate is two, and these two ultrasonic wave plates are mounted opposite the sidewall in cylinder.
Preferably, described cylinder comprises cylindrical shell and rotating shaft, and the lower end of described web member is connected with rotating shaft, and described rotating shaft is connected with transmission rig, and described ultrasonic wave plate is installed on the sidewall of cylindrical shell.
Preferably, the sidewall of described cylindrical shell is provided with opening and the door for closing opening.
Preferably, described transmission rig is gear drive.
Preferably, the material of described cylinder is any one in polyvinyl chloride, polypropylene, polymethylmethacrylate, titanium and stainless steel.
Preferably, the length of described ultrasonic wave plate is equal with the length of every face sidewall in cylinder, and the width of described ultrasonic wave plate is equal with the width of every face sidewall in cylinder.
Step (1) 1. described in the condition optimization of electrochemical deoiling process be: in degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 50g/L, and the oil removing time is 50min.
Step (1) 2. described in the condition optimization of electrochemical deoiling process be: in degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 30g/L, and the oil removing time is 15min.
The time of the barrel plating described in step (9) is 30 ~ 120min, is preferably 60min, gained coating entire bright.
Water described in above-mentioned steps is preferably the water that temperature is 20 ~ 35 DEG C.
Above-mentioned steps is all in ambient operation, and room temperature is preferably 20 ~ 35 DEG C.
The present invention has following advantage and effect relative to prior art:
1, to roll copper-plated solution nontoxic for non-cyanide alkali light provided by the invention, nonhazardous gas effusion in electroplating process.Compared with traditional additive, in solution provided by the invention, brightening agent and the agent that walks have good synergistic effect, independent interpolation brightening agent can only obtain half bright coating, and add excessively also easily cause that bonding force is bad, covering power and dispersive ability decline, produce synergy by adding of the agent that walks, brightening agent add excessive under also can ensure that bonding force is good, covering power and dispersive ability keep basically identical.The invention solves and cause the bad problem declined with covering power of bonding force without cyanogen barrel plating copper because adding brightening agent, product after simultaneously can making barrel plating reaches bright in mirror surface, is general cyanide-free copper electroplating solution or the incomparable part of cyanide-free copper electroplating solution adding conventional additive.
2, the ultrasound wave barrel in the present invention carries out pre-treatment and can save time, the energy consumption of pre-treatment and use material cost, compared with traditional pre-treatment, use ultrasound wave barrel technique can shorten oil removing time pre-treatment time and foreshorten to 10 ~ 25min by 30 ~ 50min, except oil temperature drops to 25 ~ 35 DEG C by 50 ~ 70 DEG C, the density loss 80% of acid etching, time shorten 60%, after adopting ultrasound wave barrel pre-treatment, iron-based blank surface very clean, also can there will not be the bonding force bad phenomenon such as decortication without the need to charged lower groove.
3, non-cyanide alkali light provided by the invention rolls copper-plated solution, be entire bright by the luminance brightness after its copper facing, bright in mirror surface can be reached, exceed the prussiate adding brightening agent and roll copper-plated luminance brightness, and existing cyanide-free copper electroplating is only half light, the luminance brightness effect adopting method provided by the invention can shorten follow-up electroplating time also can to reach same, alternative prussiate poisonous and harmful technique is the technique of clean and safe.
4, on the basis ensureing the bonding force between coating and matrix, solution provided by the invention and the alternative hydride systems preplating of method, realize the object that environment-protecting clean is produced.
Accompanying drawing explanation
Fig. 1 is the one-piece construction schematic diagram of ultrasound wave barrel process.
Fig. 2 is the sectional view of ultrasound wave barrel.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of ultrasound wave barrel, as depicted in figs. 1 and 2, comprise treatment trough 1, cylinder 2, web member 3, transmission rig 4, motor 5, ultrasonic wave plate 6 and ultrasonic generator, described cylinder 2 hangs in treatment trough 1 by web member 3, described cylinder 2 is connected with motor 5 by transmission rig 4, described ultrasonic wave plate 6 is installed on the sidewall of cylinder 5, and described ultrasonic wave plate 6 is connected with ultrasonic generator.Concrete, after ultrasonic wave plate 6 is installed on the sidewall of cylinder, then ultrasonic wave plate 6 directly becomes the sidewall of cylinder 5, and without any barrier between the inner chamber of cylinder 5, namely the sidewall of cylinder replaced by ultrasonic wave plate 6.In real work, after cylinder 2 put into by workpiece to be cleaned, cylinder 2 is hung in treatment trough 1 by web member 3, and makes the workpiece in the scavenging solution immersion cylinder 2 in treatment trough 1, and motor is rotated by transmission rig 4 head roll 2, meanwhile, ultrasonic wave plate 6 and ultrasonic generator produce ultrasonic wave, thus under scavenging solution and hyperacoustic dual function, thoroughly clean workpiece, this not only reduces scavenging period, also improve cleaning performance.
Described cylinder 2 cross section be regular hexagon.This structure can make to have applicable angle between the adjacent two side of cylinder 2, then cylinder is in rotation process, workpiece along cylinder 2 sidewall roll time can not produce larger collision, workpiece is avoided to be damaged, the angle be simultaneously applicable to makes workpiece have good rolling speed, to improve cleaning performance further.
The quantity of described ultrasonic wave plate 6 is two, and these two ultrasonic wave plates 6 are mounted opposite the sidewall in cylinder 2.This structure can ensure the ultrasonic wave in cylinder 2 with sufficient intensity, to ensure cleaning performance.
Described cylinder 2 comprises cylindrical shell 201 and rotating shaft 202, and the lower end of described web member 3 is connected with rotating shaft 202, and described rotating shaft 202 is connected with transmission rig 4, and described ultrasonic wave plate 6 is installed on the sidewall of cylindrical shell 201.This structure is simple, convenient manufacture, and low cost of manufacture.
The sidewall of described cylindrical shell 201 is provided with opening 7 and the door 8 for closing opening.This conveniently puts into or takes out workpiece, simultaneously in cleaning process, avoids the workpiece in cylinder to fall in treatment trough 1 when cylinder rotates.
Described transmission rig 4 is gear drive.The good stability of gear drive, ensure that the reliability of work.
The material of described cylinder 2 is polypropylene.
The length of described ultrasonic wave plate 6 is equal with the length of every face sidewall in cylinder 2, and the width of described ultrasonic wave plate 6 is equal with the width of every face sidewall in cylinder 2.This structure can ensure that ultrasonic wave plate 6 has enough intensity, simultaneously can the installation of convenience for ultrasonic ripple plate.
Embodiment 2 ~ 15
The preparation process that I, a kind of non-cyanide alkali light rolls copper-plated solution is as follows:
1. brightening agent is dissolved in pure water, prepares brightening agent solution;
2. the agent that will walk is dissolved in pure water, prepares the agent solution that walks;
3. wetting agent is dissolved in pure water, prepares wetting agent solution;
4. brightening agent solution, walk agent solution and wetting agent solution are mixed by volume, obtain additive;
5. BH-582 open cylinder agent No. 2 collocation amounts of No. 1, BH-582 open cylinder agent and 300ml are that 5 ~ 7g/L calculates with the content that described non-cyanide alkali light rolls cupric ion in the final system of copper-plated solution, the concentration of additive is 10ml, be 9 ~ 11 by pH adjusting agent (sulfuric acid and sodium hydroxide) adjust ph, be finally 1L with pure water constant volume, obtain non-cyanide alkali light and roll copper-plated solution.
The copper plating solution composition of embodiment 2 ~ 16 is as shown in table 1.
II, non-cyanide alkali light roll copper coating, specifically comprise the steps:
(1) pass-through mode 1. or mode 2. carry out electrochemical deoiling:
1. iron-based blank is placed in the without phosphorus degreasing powder solution of BH-13, carries out straight reel (Guangdong Jian Zheng electroplating device company limited, PP cylinder) electrochemical deoiling process in 55 ~ 65 DEG C; In degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 50g/L; The oil removing time is 50min;
2. iron-based blank is placed in the without phosphorus degreasing powder solution of BH-13, carries out the ultrasound wave barrel process described in embodiment 1 in 25 ~ 35 DEG C; In degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 20 ~ 40g/L30g/L, and the oil removing time is 15mim;
(2) wash: wash with water step (1) pass-through mode 1. or mode 2. carry out the iron-based blank that electrochemical deoiling obtains, remove surface residual except oil solution;
(3) activate:
1) the iron-based blank washed when step (2) is 1. carry out electrochemical deoiling by step (1) mode, activation step is: be soak 5 ~ 10min in the hydrochloric acid soln of volume percent 20% in concentration by iron-based blank clean for washing, obtain the iron-based blank activated;
2) the iron-based blank washed when step (2) is 2. carry out electrochemical deoiling by step (1) mode, activation step is: be soak 1 ~ 2min in the hydrochloric acid soln of volume percent 5% in concentration by iron-based blank clean for washing, obtain the iron-based blank activated;
(4) wash: the iron-based blank washing the activation that step (3) obtains with water, remove the acid solution of surface residual;
(5) neutralize: the sodium hydroxide solution of functional quality per-cent 1% carries out neutralizing treatment to the iron-based blank that step (4) obtains, prevent the iron-based blank activated from getting rusty, change to traditional cylinder;
(6) wash: the iron-based blank washing the activation that step (5) obtains with water, remove the alkaline solution of surface residual;
(7) activate: the iron-based blank cleaned up that step (6) obtains soaks 10s in the sulfuric acid solution liquid of volume percent 0.1%, obtain the iron-based blank activated;
(8) wash: the iron-based blank washing the activation that step (7) obtains with water, remove the acid solution of surface residual;
(9) non-cyanide alkali light barrel plating copper: more than one adopting in solvable anaerobic electrolytic copper or insoluble stainless steel, DSA coated anode are anode, the iron-based blank cleaned up in step (8) is negative electrode workpiece to be plated, be placed in above-mentioned non-cyanide alkali light and roll copper-plated solution, carry out barrel plating, the barrel plating time is 60min, gained coating entire bright; When anode is soluble, in electroplating process, in plating solution, supplement No. 1, BH-582 open cylinder agent, make the concentration of cupric ion in cyanide-free plating bath keep initial value, and regulate the pH value of plating solution to be 9 ~ 11 with sulfuric acid and potassium hydroxide.
Method A: by step (1) 1.-(2)-(3) 1.-(4) ~ (9);
Method B:(1) 2.-(2)-(3) are 2.-(4) ~ (9);
Method C: in method B, 2. step (1) 2. adopts straight reel with (3), and all the other steps are constant.
The copper electroplating method of embodiment 2 ~ 16 is as shown in table 1.
III, detection method:
Covering power is tested: temperature 55 DEG C, 0.5A/dm
2, the iron pipe of 30min, Φ 1.0 × 10.0cm, in pipe, 100% plates
Bonding force adopts 300 DEG C of thermal shock method tests.
IV, detected result, as shown in table 2:
Table 1
Note: the ratio (volume) of (1) brightening agent, walk agent and wetting agent is as follows: embodiment 4-8 and embodiment 12 are 1:1:1, embodiment 9-10 is 1:3:1, and embodiment 11 is 1:1.5:1; Embodiment 13 is ratio (volume) 1:1 of brightening agent and wetting agent;
(2) embodiment 13 is comparative examples of embodiment 8, and embodiment 4 and embodiment 12 are straight reel and ultrasound wave barrel pre-treatment comparative example.
(3) the consisting of of copper plating solution of embodiment 14 and 15: cuprous cyanide 60g/L, sodium cyanide 80g/L, sodium hydroxide 2g/L; The brightening agent of embodiment 16 is JY-50 alkalescence bright copper plating additive (Bao Lihua); Cyaniding plating method step employing method A, (9) step is cyanide copper plating.
Table 2
From embodiment 2 ~ 11, non-additive embodiment is dumb light, and what with the addition of additive is bright coating;
From embodiment 2 ~ 3, embodiment 4 ~ 11 and embodiment 14 ~ 15, add additivated cyanide-free copper electroplating adds brightening agent shiny appearance compared with cyanide electroplating;
Seen by embodiment 8 and embodiment 13 comparative example, embodiment 13 covering power that the agent that walks lacks is poor and bonding force is bad, and the agent that walks as seen has remarkably influenced to covering power and bonding force.
Seen for straight reel and ultrasound wave barrel pre-treatment comparative example by embodiment 5 and embodiment 12, adopt ultrasound wave barrel still can ensure bonding force in and time shorter situation lower except oil concentration, temperature, adopt straight reel, the effect that cannot obtain at short notice.The pre-treatment of visible employing ultrasound wave barrel is obviously better than straight reel pre-treatment.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. non-cyanide alkali light rolls a copper-plated solution, it is characterized in that comprising following composition: No. 1, BH-582 open cylinder agent, No. 2, BH-582 open cylinder agent, additive and pH value regulator;
The concentration that No. 2, BH-582 open cylinder agent is 300mL/L, the content that the addition that No. 1, BH-582 open cylinder agent rolls cupric ion in the final system of copper-plated solution with described non-cyanide alkali light after arranging in pairs or groups by itself and No. 2, BH-582 open cylinder agent is that 5 ~ 7g/L calculates, the concentration of additive is 10ml/L, and the consumption of pH value regulator maintains pH9 ~ 11 with final system and is as the criterion;
Additive by concentration be the brightening agent of 1 ~ 10g/L, wetting agent 1:(1 ~ 3 by volume of concentration to be walk agent and the concentration of 0.1 ~ 20g/L be 10 ~ 50g/L): 1 forms.
2. non-cyanide alkali light rolls copper-plated solution according to claim 1, it is characterized in that:
Described brightening agent is 1,4-butynediol, pyridinium hydroxy propyl sulfobetaine, propiolic alcohol propoxylated compounds, propiolic alcohol, propane sulfonic acid pyridinium salt, propiolic alcohol ethoxy compound, N, N-diethyl propargylamine, N, one in N-PABS, N, N-diethyl propargylamine propane sulfonic acid inner salt, butynediol ethoxy compound, butynediol propoxylated compounds, proyl sodium sulfonate and sodium allyl sulfonate or at least two kinds;
The described agent that walks is one in saltpetre, SODIUMNITRATE, hydrogen peroxide, L-glutamic acid, Sodium Thiocyanate 99, tin anhydride, tellurium dioxide, gelatin and peptone or at least two kinds;
Described wetting agent is polyoxyethylene glycol.
3. non-cyanide alkali light rolls copper-plated solution according to claim 2, it is characterized in that: described wetting agent to be molecular weight be 3000 ~ 6000 polyoxyethylene glycol.
4. non-cyanide alkali light rolls copper-plated solution according to claim 1, it is characterized in that: described wetting agent is one or both in Macrogol 3000.
5. non-cyanide alkali light rolls copper-plated solution according to claim 1, it is characterized in that: described pH value regulator is one or both in bronsted lowry acids and bases bronsted lowry.
6. non-cyanide alkali light rolls copper-plated solution according to claim 5, it is characterized in that:
Described acid is at least one in nitric acid, sulfuric acid and hydrochloric acid;
Described alkali is at least one in sodium hydroxide, potassium hydroxide and ammoniacal liquor.
7. a non-cyanide alkali light rolls copper coating, it is characterized in that: use non-cyanide alkali light described in any one of claim 1 ~ 6 to roll copper-plated solution and carry out barrel plating copper, after comprising the steps: the pre-treatment of iron-based blank, activation and washing, carry out non-cyanide alkali light barrel plating copper.
8. non-cyanide alkali light according to claim 7 rolls copper coating, it is characterized in that comprising the steps:
(1) pass-through mode 1. or mode 2. carry out electrochemical deoiling:
1. iron-based blank is placed in the without phosphorus degreasing powder solution of BH-13, carries out the process of straight reel electrochemical deoiling in 55 ~ 65 DEG C; In degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 40 ~ 60g/L; Oil removing time 40-60min;
2. iron-based blank is placed in the without phosphorus degreasing powder solution of BH-13, carries out the process of ultrasound wave barrel electrochemical deoiling in 25 ~ 35 DEG C; In degreasing powder solution, the content of the without phosphorus degreasing powder of BH-13 is 20 ~ 40g/L, oil removing time 10 ~ 20mim;
(2) wash: wash with water step (1) pass-through mode 1. or mode 2. carry out the iron-based blank that electrochemical deoiling obtains, remove surface residual except oil solution;
(3) activate:
1) the iron-based blank washed when step (2) is 1. carry out electrochemical deoiling by step (1) mode, activation step is: the clean iron-based blank of washing is soaked 5 ~ 10min in concentration is the sulphuric acid soln of volume percent 10% or the hydrochloric acid soln of volume percent 20%, obtains the iron-based blank activated;
2) the iron-based blank washed when step (2) is 2. carry out electrochemical deoiling by step (1) mode, activation step is: the clean iron-based blank of washing is soaked 1 ~ 2min in concentration is the sulphuric acid soln of volume percent 1% or the hydrochloric acid soln of volume percent 5%, obtains the iron-based blank activated;
(4) wash: the iron-based blank washing the activation that step (3) obtains with water, remove the acid solution of surface residual;
(5) neutralize: the sodium hydroxide solution of functional quality per-cent 1% carries out neutralizing treatment to the iron-based blank that step (4) obtains, prevent the iron-based blank activated from getting rusty, change to traditional cylinder;
(6) wash: the iron-based blank washing the activation that step (5) obtains with water, remove the alkaline solution of surface residual;
(7) activate: the iron-based blank cleaned up that step (6) obtains soaks 10s in the sulfuric acid solution liquid of volume percent 0.1%, obtain the iron-based blank activated;
(8) wash: the iron-based blank washing the activation that step (7) obtains with water, remove the acid solution of surface residual;
(9) non-cyanide alkali light barrel plating copper: more than one adopting in solvable anaerobic electrolytic copper or insoluble stainless steel, DSA coated anode are anode, the iron-based blank cleaned up in step (8) is negative electrode workpiece to be plated, is placed in above-mentioned non-cyanide alkali light and rolls copper-plated solution and carry out barrel plating; When anode is soluble, in electroplating process, in plating solution, supplement No. 1, BH-582 open cylinder agent, make the concentration of cupric ion in cyanide-free plating bath keep initial value, and regulate the pH value of plating solution to be 9 ~ 11; Obtain the iron-base part after barrel plating;
The structure of the ultrasound wave barrel described in step (1) is as follows: comprise treatment trough, cylinder, web member, transmission rig, motor, ultrasonic wave plate and ultrasonic generator, described cylinder hangs in treatment trough by web member, described cylinder is connected with motor by transmission rig, described ultrasonic wave plate is installed on the sidewall of cylinder, and described ultrasonic wave plate is connected with ultrasonic generator.
9. non-cyanide alkali light according to claim 8 rolls copper coating, it is characterized in that:
Described cylinder cross section be regular hexagon;
The quantity of described ultrasonic wave plate is two, and these two ultrasonic wave plates are mounted opposite the sidewall in cylinder;
Described cylinder comprises cylindrical shell and rotating shaft, and the lower end of described web member is connected with rotating shaft, and described rotating shaft is connected with transmission rig, and described ultrasonic wave plate is installed on the sidewall of cylindrical shell;
The sidewall of described cylindrical shell is provided with opening and the door for closing opening;
Described transmission rig is gear drive;
The length of described ultrasonic wave plate is equal with the length of every face sidewall in cylinder, and the width of described ultrasonic wave plate is equal with the width of every face sidewall in cylinder.
10. non-cyanide alkali light according to claim 8 rolls copper coating, it is characterized in that: also comprise conventional subsequent processing steps, by the iron-base part washing after the barrel plating that step (9) obtains, removes remaining plating solution; Carry out follow-up plating or electroless plating again.
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| WO2023126259A1 (en) | 2021-12-29 | 2023-07-06 | Basf Se | Alkaline composition for copper electroplating comprising a defect reduction agent |
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