CN101922031B - Double-plating steel belt and plating process - Google Patents

Double-plating steel belt and plating process Download PDF

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Publication number
CN101922031B
CN101922031B CN2010102450160A CN201010245016A CN101922031B CN 101922031 B CN101922031 B CN 101922031B CN 2010102450160 A CN2010102450160 A CN 2010102450160A CN 201010245016 A CN201010245016 A CN 201010245016A CN 101922031 B CN101922031 B CN 101922031B
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plating
electroplating
solution
ferro
nickel
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CN101922031A (en
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张建旭
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Sichuan Changhong Electric Co Ltd
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Sichuan Changhong Electric Co Ltd
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Abstract

The invention relates to a double-plating steel belt and a plating process, which is especially suitable for plating perforated steel belts and punched steel belts for manufacturing electrodes. The invention aims to solve the technical problems of high cost and low corrosion resistance of a steel belt on which a pure nickel layer is plated. The double-plating steel belt of the invention is characterized in that a nickel iron alloy plating of 2-4mu m is plated on a substrate steel belt, and a nickel layer of 0.5-2mu m is plated on the nickel iron alloy plating. In the invention, the nickel iron alloy plating part is used for replacing the pure nickel layer, thus the cost is lower; and simultaneously, in the plating method of the invention, a mode of dropping ferrous sulfate into a plating solution is used for replenishing the Fe2<+> ions consumed in the plating process, and the area ratio of an iron plate to a nickel plate of an anode does not need to be controlled, thus the process maintenance is simple.

Description

Double-plating steel belt and electroplating technology
Technical field
The present invention relates to be coated with the double-plating steel belt and the electroplating technology of Rhometal layer/nickel coatings, be specially adapted to the perforated steel ribbon of electrode manufacturing usefulness, the plating of Punching steel strip.
Background technology
The power supply manufacturing is widely used the following perforated steel ribbon of thickness 0.2mm, Punching steel strip as electrode connecting parts or skeleton; Common electroplating thickness is the nickel dam of 3~5 μ m on the steel band, and purpose is in order to prevent that steel strip substrate steel band in electrode manufacturing processed and battery use is corroded.
The plating pure-nickel-layer exists cost high on the steel band, and the low problem of erosion resistance.
Summary of the invention
Technical problem to be solved by this invention is in order to reduce perforated steel ribbon, Punching steel strip nickel plating cost, to improve the steel band erosion resistance simultaneously.
Technical scheme of the present invention is: ferro-nickel alloy plating partly replaces pure nickel dam, is coated with the ferro-nickel alloy plating of 2-4 μ m on the matrix steel band; Be coated with the nickel dam of 0.5~2 μ m above the ferro-nickel alloy plating.
Wherein, iron-holder is 25~30% in the ferro-nickel alloy plating, and iron level can influence coating mechanical property (mainly be hardness, and internal stress), and the too high internal stress of iron level is big, is unfavorable for the electrode manufacturing.
Because double-deck coating have potential difference between ferro-nickel alloy plating and the nickel dam, and porosity is relatively low, therefore, when the generation corrosion, the preferential and middle ferro-nickel alloy plating of meeting reacts, thereby reaches the purpose of protection matrix, and the matrix corrosion resistance nature is improved.
Electro-plating method of the present invention is after steel band is cleaned out, electronickelling behind the first ferro-nickel alloy electroplating.
It should be noted that the present invention can not first nickeling layer after the ferro-nickel alloy layer because Rhometal can produce yellow spotting on the surface, adopt behind the first ferro-nickel alloy layer method of nickel plating can avoid producing yellow spotting (corrosion product of iron).
In order to eliminate a last operation solution, avoid subsequent processing is impacted, or influence the last visual appearance of coating, can after each operation, increase cleaning step.
Wherein, the cleaning steel strip surface can adopt rusty stain and the oxide debris that existing method is deoiled and piece surface is plated in the acid etch removing.
The technology that plating nickel on surface iron-zinc alloy coatings such as bicycle rim, copper coin are arranged in the prior art; Usually adopt the combined anode of nickel plate+pure iron plate; Adopt the area ratio of nickel plate, pure iron plate to control the ratio of nickel ion and iron ion in the electroplating solution, have the problem of operational difficulty.And, a ferro-nickel alloy, the coating corrosion resistance is not enough, and the surface can produce yellow spotting (corrosion product of iron) very soon.
Ferro-nickel alloy electroplating of the present invention does not adopt the combined anode of existing nickel plate+pure iron, is single anode and adopt the nickel plate, is employed in and drips FeSO in the electrolytic solution 4The mode of solution is replenished the iron that consumes in the electrolytic process, and is through the ratio of nickel ion and iron ion in the rate of addition control electrolytic solution, simple to operate.
The electroplating solution prescription is:
NiSO 4·7H 2O?220~250g/L;
H 3BO 330~40g/L;
NaC10~15g/L;
FeSO 4·7H 2O?25~35g/L;
Sodium lauryl sulphate 0.1~0.3g/L;
Stablizer a small amount of (stablizer used herein generally adopts xitix 1~2g/L, also can use commercially available commodity stablizer, like the BH stablizer of Guangzhou the second light industry bureau production).Can also use Hydrocerol A, glucono-, tartrate and composite mixture thereof.
Adopting the purpose of stablizer is to avoid the ferrous ion in the plating bath to be oxidized to ferric ion, thereby causes coating fragility to increase, and mechanical property reduces, even produces burr.
It is that 20%~25% solution slowly splashes in the electroplating solution that ferrous sulfate is configured to concentration, replenishes the Fe that consumes in the electroplating process 2+Ion makes Fe 2+Concentration maintains 5~7g/L.
One of embodiment, during ferro-nickel alloy electroplating, at the other intake chute that is provided with of coating bath, plating tank and intake chute through two liquid delivery tubes together with, form continuously and circulate; Copperas solution is accomplished at intake chute and is dripped, and is delivered to plating tank through circulation tube and replenishes the Fe that consumes in the electrolytic process 2+, see Fig. 1 for details.
In order to prevent that burr and pin hole from appearring in coating, in the middle of the liquid delivery tube together with plating tank and intake chute filtration unit is set, make to get into intake chute again behind the electroplate liquid solids removed by filtration impurity in the plating tank; Simultaneously, it is reinforced that intake chute is accomplished copperas solution, gets into plating tank after the filtration again.
Wherein, electroplating temperature is advisable at 50~70 ℃, current density 2~10A/dm 2, tape running speed can will be adjusted according to required electrolytic coating thickness.Temperature is low excessively, and electroplating velocity is slow, burns easily, and temperature is too high, the easy oxygenolysis of stablizer, and ferrous iron is oxidized to ferric iron easily.
The power supply of electroplating usefulness can adopt high frequency switch power or other power supply.
Wherein, electronickelling can be adopted general electronickelling prescription and electronickelling technology.
During practical implementation, steel plate through deoil, water cleans, the anode and cathode co-electrolysis deoils, water cleaning, acid etch, water cleaning, ferro-nickel alloy electroplating, water cleaning, electronickelling, water are cleaned, alkali neutralization, dry, rolling.
Beneficial effect of the present invention:
Ferro-nickel alloy plating partly replaces pure nickel dam cost lower (iron-holder is 25~30% in the ferro-nickel alloy plating, and the price of iron is very cheap, and price is about 4 yuan/kg at present, and the price of nickel is higher, is about 190 yuan/kg at present).
In addition, electro-plating method of the present invention adopts ferrous sulfate to splash into the mode in the electroplating solution, replenishes the Fe that consumes in the electroplating process 2+Ion need not controlled the area ratio of anodic iron plate and nickel plate, and process maintenance is simple.
Embodiment
An embodiment of the invention may further comprise the steps:
(1) deoil: adopt all kinds of acidity or alkaline degreasing solution all can, purpose is to remove the greasy dirt of steel strip surface.
(2) water cleans;
(3) the anode and cathode co-electrolysis deoils;
(4) water cleans;
(5) acid etch; Purpose is rusty stain and the oxide debris of removing by the plating piece surface;
(6) water cleans;
(7) ferro-nickel alloy electroplating: the electroplating solution prescription is NiSO 47H 2O 220~250g/L; H 3BO 330~40g/L; NaCl0~15g/L, FeSO 47H 2O 25~35g/L; Sodium lauryl sulphate 0.1~0.3g/L, stablizer is a small amount of, and (stablizer used herein generally adopts xitix 1~2g/L, also can use commercially available commodity stablizer; BH stablizer like the production of Guangzhou the second light industry bureau) temperature is 50~70 ℃, current density 2~10A/dm 2, tape running speed can will be adjusted according to thickness.Anode material adopts single sheet nickel, and it is 20%~25% the solution adding electroplating solution that slowly instils that ferrous sulfate is configured to concentration.Electroplate the power supply use as high frequency switch power but be not limited to high frequency switch power.
Metallic nickel has very strong passivation ability, in order to prevent the nickel anode passivation, adds the anode promoting agent, can promote anode dissolution, guarantees that the normal of nickel ion replenishes.Usually with NaCl, nickelous chloride etc., when anode nickel became nickel ion and leaves anode, the existence owing to cl ions form nickelous chloride very soon, and the nickelous chloride good water solubility made like this nickel ion be diffused into plating bath inside rapidly from the positive column, thereby prevents anode passivation.But adding too much to make anode dissolution too fast.
Adding tensio-active agents such as sodium lauryl sulphate, n-octyl sodium sulfate is in order to prevent that coating from producing pin hole, to add the too much very few coating surface that all can make and grow dim.
Boric acid H 3BO 3Be buffer reagent, have the effect of stablizing the pH value, the pH value is controlled at 3.0~5.0 (preferred 3.5~4.5).But the amount of boric acid too much can cause burr and coarse.
(8) water cleans
(9) electronickelling: can adopt general electronickelling prescription and technology electronickelling 0.5~2 μ m.
(10) water cleans
(11) neutralization: steel band is passed through from the pH value is 8~12 basic soln.Purpose is that steel strip surface is neutralized into alkaline state, prevents corrosion in storage, the use.
(12) drying: steel band drawn in the baking oven pass through, oven dry.
(13) rolling.
Below through the mode of specific embodiment the present invention is done further detailed description.
Embodiment 1: electroplating thickness is 0.1mm, and width is the perforated steel ribbon of 23mm
(1) deoil: adopt all kinds of acidity or alkaline degreasing solution all can, purpose is to remove the greasy dirt of steel strip surface.
(2) water cleans;
(3) the anode and cathode co-electrolysis deoils;
(4) water cleans;
(5) acid etch;
(6) water cleans;
(7) ferro-nickel alloy electroplating: the electroplating solution prescription is NiSO 47H 2O 220g/L; H 3BO 330g/L; NaCl 12g/L, FeSO 47H 2O 28g/L, sodium lauryl sulphate 0.1g/L, BH stablizer 18ml/L, 55 ℃ of temperature, current density 5A/dm 2, electroplating time 3min.
Rhometal thickness 2.3 μ m.
(8) water cleans
(9) electronickelling: general electronickelling prescription and technology electronickelling 0.5~2 μ m
(10) water cleans
(11) neutralization: steel band is passed through from the pH value is 8~12 basic soln.
(12) drying: steel band drawn in the baking oven pass through, oven dry.
(13) rolling.
Steel band is immersed in 7d in 20% the sodium hydroxide solution, temperature is controlled at 65 ± 2 ℃, and coating does not have corrosion.
It is qualified that bend test method detects the steel band bonding force.
Embodiment 2: electroplating thickness is 0.1mm, and width is the Punching steel strip of 180mm
(1) deoil: adopt all kinds of acidity or alkaline degreasing solution all can, purpose is to remove the greasy dirt of steel strip surface.
(2) water cleans;
(3) the anode and cathode co-electrolysis deoils;
(4) water cleans;
(5) acid etch;
(6) water cleans;
(7) ferro-nickel alloy electroplating: the electroplating solution prescription is NiSO 47H 2O240g/L; H 3BO 332g/L; NaCl 14g/L, FeSO 47H 2O31g/L, sodium lauryl sulphate 0.2g/L, xitix 1.5g/L) 65 ℃ of temperature, current density 8A/dm 2, electroplating time 2min.
Rhometal thickness is 3.1 μ m.
(8) water cleans
(9) electronickelling: general electronickelling prescription and technology electronickelling 0.5~2 μ m
(10) water cleans
(11) neutralization: steel band is passed through from pH value is 8~12 basic soln.
(12) drying: steel band drawn in the baking oven pass through, oven dry.
(13) rolling.
Steel band is immersed in 7d in 20% the sodium hydroxide solution, temperature is controlled at 65 ± 2 ℃, and coating does not have corrosion.
It is qualified that bend test method detects the steel band bonding force.
Embodiment 3: electroplating thickness is 0.1mm, and width is the perforated steel ribbon of 160mm
(1) deoil: adopt all kinds of acidity or alkaline degreasing solution all can, purpose is to remove the greasy dirt of steel strip surface.
(2) water cleans;
(3) the anode and cathode co-electrolysis deoils;
(4) water cleans;
(5) acid etch;
(6) water cleans;
(7) ferro-nickel alloy electroplating: the electroplating solution prescription is NiSO 47H 2O245g/L; H 3BO 335g/L; NaCl 13g/L, FeSO 47H 2Og/L, sodium lauryl sulphate 0.15g/L, xitix 1.8/L) 62 ℃ of temperature, current density 5A/dm 2, electroplating time 3min.
Rhometal thickness is 2.5 μ m.
(8) water cleans
(9) electronickelling: general electronickelling prescription and technology electronickelling 0.5~2 μ m
(10) water cleans
(11) neutralization: steel band is passed through from pH value is 8~12 basic soln.
(12) drying: steel band drawn in the baking oven pass through, oven dry.
(13) rolling.
Steel band is immersed in 7d in 20% the sodium hydroxide solution, temperature is controlled at 65 ± 2 ℃, and coating does not have corrosion.
It is qualified that bend test method detects the steel band bonding force.

Claims (8)

1. electrode is used double-plating steel belt, it is characterized in that: the ferro-nickel alloy plating that is coated with 2-4 μ m on the matrix steel band; Be coated with the nickel dam of 0.5~2 μ m above the ferro-nickel alloy plating; Iron-holder is 25~30% in the ferro-nickel alloy plating;
The electroplating solution prescription is during ferro-nickel alloy electroplating:
NiSO 4·7H 2O?220~250g/L;
H 3BO 330~40g/L;
NaCl?0~15g/L;
FeSO 4·7H 2O?25~35g/L;
Sodium lauryl sulphate 0.1~0.3g/L;
Stablizer xitix 1~2g/L.
2. the described electrode of claim 1 is characterized in that with the electroplating technology of double-plating steel belt: after steel strip surface is cleaned out, and electronickelling behind the first ferro-nickel alloy electroplating.
3. electroplating technology according to claim 2 is characterized in that: it is single anode that ferro-nickel alloy electroplating coating adopts the nickel plate, through in electrolytic solution, dripping FeSO 4The mode of solution is replenished the Fe that consumes in the electrolytic process 2+, make Fe 2+Concentration maintains 5~7g/L.
4. electroplating technology according to claim 3 is characterized in that: during ferro-nickel alloy electroplating, at the other intake chute that is provided with of coating bath, plating tank and intake chute through two liquid delivery tubes together with, form continuously and circulate; Copperas solution is accomplished at intake chute and is dripped, and is delivered to plating tank through circulation tube and replenishes the Fe that consumes in the electrolytic process 2+
5. electroplating technology according to claim 4 is characterized in that: together with in the middle of the liquid delivery tube of plating tank and intake chute filtration unit is set, makes to get into intake chute again behind the electroplate liquid solids removed by filtration impurity in the plating tank; Simultaneously, it is reinforced that intake chute is accomplished copperas solution, gets into plating tank after the filtration again.
6. electroplating technology according to claim 5 is characterized in that: through dripping FeSO 4Fe in the speed control electrolytic solution of solution 2+Concentration.
7. electroplating technology according to claim 6 is characterized in that: the FeSO of dropping 4The mass percent concentration of solution is 20%~25% solution.
8. according to each described electroplating technology of claim 2-7, it is characterized in that: 50~70 ℃ of electroplating temperatures, current density 2~10A/dm 2
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JP6200719B2 (en) * 2013-07-31 2017-09-20 東洋鋼鈑株式会社 Method for producing surface-treated steel sheet for battery container
JP6688564B2 (en) * 2015-05-28 2020-04-28 昭和電線ケーブルシステム株式会社 Method for manufacturing oxide superconducting wire
JP6176514B1 (en) * 2016-01-19 2017-08-09 株式会社YC・Primarily Comb manufacturing method
CN105506698A (en) * 2016-02-19 2016-04-20 苏州市华婷特种电镀有限公司 Electroplating piece with nickel coating on surface
CN109868952A (en) * 2017-12-02 2019-06-11 鹤山市鸿图铁艺实业有限公司 A kind of manufacturing process of guardrail metal tube
CN109576745B (en) * 2019-01-31 2020-10-30 徐九生 Manufacturing process of conductive ball

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JPH02263990A (en) * 1989-04-04 1990-10-26 Yamaha Corp Electroplating method for iron-nickel alloy plating film
CN101532155B (en) * 2009-02-26 2010-08-11 上海造币有限公司 Application process of multi-layer electroplated coinage materials and products thereof
CN101760767B (en) * 2009-12-03 2011-09-28 四川长虹电器股份有限公司 Method for electroplating steel strip with nickel

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