CN103668374B - A kind of wide cut stainless steel band one side copper coating and electroplating bath - Google Patents
A kind of wide cut stainless steel band one side copper coating and electroplating bath Download PDFInfo
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- CN103668374B CN103668374B CN201310704063.0A CN201310704063A CN103668374B CN 103668374 B CN103668374 B CN 103668374B CN 201310704063 A CN201310704063 A CN 201310704063A CN 103668374 B CN103668374 B CN 103668374B
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Abstract
The invention discloses a kind of wide cut stainless steel band one side copper coating and electroplating bath, the method is after the pre-surfacing oil removing of substrate stainless steel band, to activate; In the pre-surfacing of substrate stainless steel band activating, first plate nickel preplating, then plate dark nickel, finally copper facing in alkaline non-cyanide plating solution; After the stainless steel band passivation after copper facing, drying, to obtain final product; What copper facing adopted is improved electroplating bath, described electroplating bath is to seal at least two transmission transfer rollers have been installed respectively on two cell walls at the transmission entrance and exit place of electroplating bath, this device can ensure trough liquid level, prevent the coating scratch of stainless steel band, is specially adapted to the continuous one side copper facing of the banded stainless steel band of wide cut; The inventive method safety and environmental protection, low cost, can be at a high speed by continuous wide cut stainless steel band one side copper facing; The single-side stainless steel band coating surface that the method makes is light, fine and close evenly, and corrosion resistance is strong, and coating conductance is high, and resistance to punching performance is good, meets the demand of electronics, military project, can suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of wide cut stainless steel band one side copper coating and electroplating bath, belong to metal plating neckTerritory.
Background technology
One side cover copper stainless steel material due to its light, the feature such as hardness is high, corrosion resistance is strong, copper layer good conductivity,To be widely used in electronic information material, ornament materials and military project material industry. To copper-plating technique, both at home and abroadAll compare many research. At present main copper facing mode has: cyanide electroplating, pyrophosphate copper plating, sulfuric acidSalt copper facing, ethylenediamine copper facing, fluoboric acid copper facing, the copper facing of citric acid-tartaric acid, HEDP copper facing and amino sulphurAcid copper facing system etc. Cyanide copper plating crystallization is careful, adhesion good, all plating property, leveling property, stability of plating solutionAlso very good, but cyanide has severe toxicity, waste liquid is difficult, and environmental pollution is serious. The plating of light pyrophosphateCopper crystallization is careful, has good dispersibility and covering power, but its cost is high, phosphate can occur long-pendingTired, deposition velocity is declined, waste water control difficulty. Citric acid-tartaric acid copper facing system also on a small quantity for the production of,But adhesion is undesirable, plating solution cost is high, easily mildews. All because there is different defects in other several techniques,Be not applied to large-scale production.
The substrate at present research institute of copper facing system being adopted is taking ordinary carbon steel as main, and to stainless steel surfaces copper facingResearch also very few. Stainless steel is because its chemical composition and ordinary carbon steel have larger difference, and stainless steelSurface very easily generates fine and close oxide-film, in electroplating process, is affected, and causes the problems such as coating peeling. StainlessThe elements such as the chromium in steel are penetrated in copper electrolyte, easily cause that plating solution is poisoning.
Patent CN101545126A discloses a kind of for surface coating of high chrome steel preparation method, comprise degreasing,Cold rinse, the weak corrosion+nickel plating of weak burn into, cold rinse, bronze (copper-tin alloy) electroplating, cold rinse, passivation, cold and hot clearWash, soak molybdenum. Mainly for improving the antisticking performance of oil sleeve joint, realize on oil sleeve joint shackle completeProperty. This patent is mainly in rack plating technique, and is not suitable for stainless steel band one side copperizing continuously.
One side cover copper stainless steel material due to its light, the feature such as hardness is high, corrosion resistance is strong, copper layer good conductivity,To be widely used in electronic information material, ornament materials and military project material industry. To copper-plating technique, both at home and abroadAll compare many research. The substrate at present research institute of copper facing system being adopted is taking ordinary carbon steel as main,And it is also very few to the copper-plated research of stainless steel surfaces. Wide cut stainless steel band continuous electroplating exists CURRENT DISTRIBUTION notAll, affect uniformity, corrosion resistance and the aesthetic problem of thickness of coating. Therefore, must come by new methodSolve wide cut stainless steel band one side and cover continuously the problem that copper exists.
Summary of the invention
The present invention is directed to metal-plated process for copper of the prior art, exist plating solution to contain harmful toxic matter, waste liquid is difficult,Environmental pollution is serious, and cost is high, and copper coating is in conjunction with poor effect, particularly coating peeling when stainless steel copper facing,Plating solution is very easily poisoning, and length consuming time, the defect such as can not produce continuously, object be to provide a kind of safety and environmental protection,Low cost, can be at a high speed by continuous wide cut stainless steel band one side copper coating, the single-side stainless steel that the method makesEvenly light, fine and close of band coating surface, corrosion resistance is strong, and coating conductance is high, and resistance to punching performance is good, meetsThe demand of electronics, military project, can suitability for industrialized production.
Another object of the present invention be to provide a kind of in stainless steel band copper facing process, can ensure trough liquid level,Prevent the coating scratch of stainless steel band, be specially adapted to the copper-plated plating of the banded continuous one side of stainless steel band of wide cutGroove.
The invention provides the copper coating of a kind of wide cut stainless steel band one side, the method is by substrate stainless steel bandPre-surfacing oil removing after activate; In the pre-surfacing of substrate stainless steel band activating, first plate nickel preplating, then plate dark nickel,Last copper facing in the electroplating bath that is provided with multistage rolling wall sealing device, described electroplating bath is at transmission entrance and exitOn two cell walls at place, at least two transmission transfer rollers have been installed in sealing respectively; When plating, in described electroplating bath, be equipped withAlkaline non-cyanide plating solution, adjusting current density is 2～8A/dm2, stainless steel band with preplating facing to described electroplating bathThe electrode that bottom land arranges, transmits from sealing between two parallel transmission transfer rollers, is parallel to bottom land through coating bath,Carry out one side copper facing; After the stainless steel band passivation after copper facing, drying, to obtain final product;
Wherein, every liter of alkaline non-cyanide plating solution comprises following component: copper sulphate 40～80g; Potassium hydroxide 10～50g;Carboxylic acid sylvite 10～50g; Complexing agent 6～60g; Dispersant 6～60g; Brightener 0.8～8g.
Described current density is preferably 2～6A/dm2。
Described complexing agent is in potassium tartrate, biuret, glycerine, HEDP or EDTAThe compound of one or more and potassium citrate.
In described complexing agent, the mass percent of potassium citrate is 25～50%.
Described brightener is the one in naphthalenedisulfonic acid, asccharin, cystine, acetyl thiourea or acrylic thiocarbamideOr several and compound sodium thiosulfate.
In described brightener, the mass percent of sodium thiosulfate is 16～50%.
Described dispersant is a kind of or several in polyethylene glycol, polymine, poly-two sulphur two ethane sulfonic acid sodiumKind.
Described alkaline non-cyanide plating solution pH is 8.0～10.0.
Described copper facing temperature is 45～70 DEG C, and the time is 1～20min.
Described activation is the sulfuric acid of substrate stainless steel band first being used to 2～20wt%, is at 15～35 DEG C in temperature,Soak 0.5～10min; Use again the hydrochloric acid of 2～20wt%, at 15～35 DEG C, using substrate stainless steel band as the moonThe utmost point, inert electrode is anode, is 0.1～5A/dm in current density2Lower electrolysis 0.5～8min.
Described nickel preplating plating condition is: electroplate liquid: every liter of electroplate liquid comprise 30～300g nickel chloride andThe concentrated hydrochloric acid of 30～300mL; PH≤1, temperature is 15～35 DEG C, anode is pure nickel piece; In current density be0.5～5A/dm2Lower plating 0.5～8min.
The dark nickel plating of described plating condition is: electroplate liquid: every liter of electroplate liquid comprise 180～300g nickelous sulfate,15～50g nickel chloride and 15～50g boric acid; PH is 2.8～4.8, and temperature is 40～65 DEG C, and anode is pure nickel piece;Be 0.5～6A/dm in current density2Lower plating 0.5～10min.
Described substrate stainless steel band is that thickness is 0.05～1mm, and 2 series that width is 10～1200mm are stainlessSteel band, 3 series stainless steel bands or 4 series stainless steel bands.
Described substrate stainless steel band is preferably 201 stainless steel bands, 304 stainless steel bands or 430 stainless steel bands.
Described oil removing is at 45～65 DEG C, first uses degreasing powder and detergent washing 0.5～5min; Again at electrolyteIn, be 1～5A/dm in current density2Under, using stainless steel band as negative electrode, inert electrode is anode, electrolysis0.5～10min, then using stainless steel band as anode, inert electrode is negative electrode, electrolysis 0.5～10min; Wherein,Every liter of electrolyte comprises NaOH 30～100g, sodium carbonate 20～80g and tertiary sodium phosphate 20～80g.
Described passivation be stainless steel band that copper facing is completed at 25～40 DEG C, the benzo that is 3～10g/L by concentrationTriazole soaks 0.5～5min.
The wide cut one side copper facing stainless steel band that the inventive method makes, the single surface of substrate stainless steel band one plating successivelyThere are nickel coating and copper coating; Described copper coating thickness is 0.5～15 μ m, and surface roughness is Ra≤0.1 μ m; InstituteState nickel coating and comprise pre-nickel plating and dark nickel dam, nickel coating thickness is 0.1～4 μ m.
It is a kind of for the copper-plated electroplating bath of wide cut stainless steel band one side that the present invention also provides, and described electroplating bath existsOn two cell walls at the transmission entrance and exit place of electroplating bath, at least 2 transmission transfer rollers have been installed in sealing respectively.
Described transmission transfer roller is made up of rubber axle sleeve coated metal axle core.
Preferred electroplating bath seals and has installed 4 respectively on two cell walls at the transmission entrance and exit place of electroplating bathRoot transmission transfer roller.
Parallel and sealing contact between described transmission transfer roller and transmission transfer roller.
Between described transmission transfer roller and cell wall, seal and contact.
When described electroplating bath is electroplated, sheet metal strip transmits from sealing between two parallel transmission transfer rollers, parallelPass coating bath in bottom land.
Wide cut stainless steel band one side of the present invention copper coating comprises the following steps:
(1) electrochemical deoiling
With degreasing powder and washing agent at 45～65 DEG C, washing 0.5～5min;
Wherein, in every liter of washings, contain degreasing powder 40～100g and washing agent 0.1～10mL;
(2) electrolytic degreasing
Electrolyte: every liter of electroplate liquid comprises NaOH 30～100g, sodium carbonate 20～80g and tertiary sodium phosphate20～80g; Temperature is 45～65 DEG C, and current density is 1～5A/dm2；
First, using the substrate stainless steel band after electrochemical deoiling as negative electrode, inert electrode is anode, electrolysis 0.5～10Min; Using substrate stainless steel band as anode, inert electrode is negative electrode, electrolysis 0.5～10min again;
(3) chemical activation
The sulfuric acid that is 2～20% by concentration mass percentage concentration soaks 0.5～10min at 15～35 DEG C;
(4) electrolysis, activation
Electrolyte is that mass percent concentration is 2～20% hydrochloric acid, using the substrate stainless steel band after activating asNegative electrode, inert electrode is anode, temperature is 15～35 DEG C; Be 0.1～5A/dm in current density2Lower electrolysis0.5～8min；
(5) nickel preplating
Electroplate liquid: every liter of electroplate liquid comprises 30～300g nickel chloride and 30～300mL concentrated hydrochloric acid; PH is less than1, adopt pure nickel piece as anode, temperature is 15～35 DEG C; Be 0.5～5A/dm in current density2Lower plating0.5～8min；
(6) plate dark nickel
Electroplate liquid: every liter of electroplate liquid comprises 180～300g nickelous sulfate, 15～50g nickel chloride and 15～50g boric acid;PH is 2.8～4.8, and adopting pure nickel piece is anode, and temperature is 40～65 DEG C; Be 0.5～6A/dm in current density2Lower plating 0.5～10min;
(7) alkaline non-cyanide high speed copper facing
Adopt electroplating bath shown in accompanying drawing 1 to electroplate,
Electroplate liquid: every liter of alkaline non-cyanide plating solution comprises copper sulphate 40～80g, potassium hydroxide 10～50g, carboxylic acidSylvite 10～50g, complexing agent 6～60g, dispersant 6～60g, brightener 0.8～8g; PH is 8.0～10.0,Adopt high-purity copper billet as anode, temperature is 45～70 DEG C, is 2～8A/dm in current density2Lower plating1～20min；
Described complexing agent is in potassium tartrate, biuret, glycerine, HEDP or EDTAThe compound of one or more and potassium citrate, in described compound the mass percent of potassium citrate be 25～50%；
Described dispersant is a kind of or several in polyethylene glycol, polymine, poly-two sulphur two ethane sulfonic acid sodiumKind;
Described brightener is the one in naphthalenedisulfonic acid, asccharin, cystine, acetyl thiourea or acrylic thiocarbamideOr several and compound sodium thiosulfate, in described compound the mass percent of sodium thiosulfate be 16～50%；
(8) passivation
In the BTA that is 3～10g/L in concentration by the stainless steel band after copper facing, at 25～40 DEG C, soakBubble 0.5～5min;
(9) heat treatment
In the special atmosphere oven of 80～260 DEG C, toast 2～60min;
Between above-mentioned two processing steps, clean up by deionized water.
Know-why of the present invention and beneficial effect: the inventive method is first removed dry by the pre-surfacing of stainless steel bandOnly, activation, plates the nickel dam of 0.1～4 μ m thickness, first plates pre-nickel plating, pre-nickel plating and activation stainlessSteel strip surface, in conjunction with good, can contact with stainless steel band surface by air-isolation, prevents from again forming oxide-film; AgainFurther plate dark nickel, made up the unsound defect of pre-nickel plating, further improve binding force of cladding material, simultaneouslyAlso prevent that the element solution pervasions such as stainless steel surfaces iron, chromium are in the copper plating solution of subsequent processing; Plating of the present inventionIn copper process, adopt by repetition test develop obtain without cyanogen high-speed plating copper electrolyte, this plating solution employing highly efficiency compositionalComplexing agent, has strengthened the complexing effect to copper ion greatly, and combines the peptizaiton of dispersant, by networkThe copper ion closing is dispersed in plating solution better, in the bath system that effectively prevents from being alkaline at high current densityThe problem that lower excessive free copper ion easily produces precipitation, has realized the plating under high current density, with thisWhen bright plating solution copper facing, current density can reach 8A/dm2, optimum current density is 2～6A/dm2, electroplateTime shortens greatly, reached high speed copper facing, and prior art neutral and alkali copper facing system current density is all very little,Generally be no more than 2A/dm2; What electroplate liquid of the present invention was selected is all cheap raw material, and these raw material components are compositeAfter reach good effect, avoided use cyanide, pyrophosphate etc. poisonous, the plating solution of contaminated environment, electricityIn plating solution, also add composite brightener, increased coating brightness, made coating surface light, reduced surface slightlyRugosity, is controlled in 0.1 μ m roughness Ra; The electrolytic cell assembly that the present invention is also combined with copper facingImprove, in the transmission direction of electrolytic cell, multistage rolling wall sealing device has been installed, by conventional metals bandAnd the sliding friction between rubber weather strip has converted the rolling friction between sheet metal strip and transmission transfer roller to, keeps awayExempt from scuffing, also reduced the tension of sheet metal strip; Meanwhile, multistage rolling seal device roller was being producedIn journey, not stall is moving, if there is impurity absorption, it is upper, can be by impurity removes outside coating bath time, keeps productionClean stable; This device has been realized continued operation, is particularly suitable for the continuous one-side electroplating of wide cut sheet metal strip;In sum, the single-side stainless steel band coating surface that the inventive method makes is light, fine and close evenly, and corrosion resistance is strong,Coating conductance is high, and resistance to punching performance is good, meets the demand of electronics, military project, can suitability for industrialized production.
Brief description of the drawings
[Fig. 1] is the electroplating bath main cross section figure that is provided with multistage rolling wall sealing device: 1 is sheet metal strip; 2 for passingMoving transfer roller; 3 is cell wall; 4 is electroplating bath; 5 is electrode.
[Fig. 2] is the electroplating bath A view that is provided with multistage rolling wall sealing device: 1 is sheet metal strip; 8 is rubberAxle sleeve; 7 is metal shaft core; 3 is plating wall.
[Fig. 3] is provided with transmission transfer roller profile in multistage rolling seal device: 1 is sheet metal strip; 8 is rubberAxle sleeve; 7 is metal shaft core.
[Fig. 4] is provided with transfer roller side view in multistage rolling seal device: 8 is rubber axle sleeve; 7 is metal shaft core.
[Fig. 5] is the one side copper facing stainless steel band that method of the present invention makes: 10 is copper plate; 11 is dark nickel dam;12 is pre-nickel plating; 13 is substrate stainless steel band.
Detailed description of the invention
Following examples are intended to illustrate the present invention, instead of further restriction to protection domain of the present invention.
Embodiment 1
Adopt the mode of horizontal transmission, electroplate one side on the lower, taking 430 stainless steel bands as base material, thickness is0.25mm, width is 600mm, adopts following technique, and it is processed.
(1) electrochemical deoiling
Process conditions are: in every liter of washings, comprise degreasing powder 60g, washing agent 5mL; Temperature is 55 DEG C,Time is 3min; Clean by hot water wash;
(2) electrolytic degreasing
Process conditions are: electrolyte: every liter of electrolyte comprises NaOH 60g, sodium carbonate 40g, tricresyl phosphateSodium 30g; Temperature is 55 DEG C, and current density is 3A/dm2；
First, using stainless steel band as negative electrode, inert electrode is anode, electrolytic degreasing 5min; Again by stainless steel bandAs anode, inert electrode is negative electrode, oil removing 5min; First clean by hot water wash, then rinse well with clear water;
(3) chemical activation
Process conditions are: the sulfuric acid of 10wt%, and temperature is 25 DEG C, soak time is 5min;
Rinse well with clear water;
(4) electrolysis, activation
Process conditions are: electrolyte: the hydrochloric acid of 10wt%; Temperature is 25 DEG C, using stainless steel band as negative electrode,Inert electrode is anode; Be 3A/dm in current density2Lower electrolysis 4min;
After electrolysis, rinse well with clear water;
(5) nickel preplating
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises nickel chloride 120g, concentrated hydrochloric acid 180mL; PH is littleIn 1, temperature is 25 DEG C, adopts pure nickel piece as anode; Be 3A/dm in current density2Lower plating 1min;
After plating completes, rinse well with clear water;
(6) plate dark nickel
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises nickelous sulfate 240g, nickel chloride 35g, boric acid 30g;PH is 4.3, and temperature is 50 DEG C, and adopting pure nickel piece is anode; Be 3A/dm in current density2Lower plating 5min;
After plating completes, rinse well with clear water;
(7) alkaline non-cyanide high speed copper facing
Adopt electroplating bath shown in Fig. 1 to electroplate,
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises copper sulphate 60g; Potassium hydroxide 30g; Carboxylic acid potassiumSalt 30g; Potassium tartrate, biuret and natrium citricum in mass ratio 1:1:1 are composite, get 30g; Polyethylene glycol andPolymine sodium in mass ratio 1:1 is composite, gets 25g; Naphthalenedisulfonic acid, asccharin and sodium thiosulfate are by qualityMore composite than 1:1:1, get 4g; PH is 8.8, and temperature is 55 DEG C, adopts high-purity copper billet as anode; At electricityCurrent density is 3A/dm2Lower plating 5min;
After plating completes, rinse well with clear water;
(8) passivation
Process conditions are: benzotriazole 5g/L, and temperature is 30 DEG C, the time is 2min;
First use hot water wash, then rinse well with clear water;
(9) heat treatment
In the nitrogen protection stove of 180 DEG C, toast 10min.
Prepared one side copper facing stainless steel band surface is observed, find surface-brightening, inviolateness, without bubbling,Without phenomenons such as line.
With extra coarse degree tester, prepared one side copper facing stainless steel band surface is tested, result shows its tableThe coarse plating of face is Ra≤0.1 μ m.
By hundred lattice methods, the one side copper facing stainless steel band of preparation is tested, coating is without coming off.
The stainless steel band making carries out neutral salt spray test, and 24 hours without rust spot.
Embodiment 2
Adopt the mode of horizontal transmission, electroplate one side on the lower, taking 201 stainless steel bands as base material, thickness is0.15mm, width is 120mm, adopts following technique, and it is processed.
(1) electrochemical deoiling
Process conditions are: in every liter of washings, comprise degreasing powder 60g, washing agent 5mL; Temperature is 55 DEG C,Time is 3min;
Clean by hot water wash;
(2) electrolytic degreasing
Process conditions are: electrolyte: every liter of electrolyte comprises NaOH 60g, sodium carbonate 40g, tricresyl phosphateSodium 30g; Temperature is 50 DEG C, and current density is 3A/dm2；
First, using stainless steel band as negative electrode, inert electrode is anode, electrolytic degreasing 5min; Again by stainless steel bandAs anode, inert electrode is negative electrode, oil removing 5min;
First clean by hot water wash, then rinse well with clear water;
(3) chemical activation
Process conditions are: the sulfuric acid of 10wt%, and temperature is 25 DEG C, soak time is 5min;
Rinse well with clear water;
(4) electrolysis, activation
Process conditions are: electrolyte: the hydrochloric acid of 10wt%; Temperature is 25 DEG C, using stainless steel band as negative electrode,Inert electrode is anode; Be 3A/dm in current density2Lower electrolysis 4min;
After electrolysis completes, rinse well with clear water;
(5) nickel preplating
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises: nickel chloride 100g, concentrated hydrochloric acid 180mL; PHBe less than 1, temperature is 20 DEG C, adopts pure nickel piece as anode; Be 1A/dm in current density2Lower plating 2min;
After plating completes, rinse well with clear water;
(6) plate dark nickel
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises nickelous sulfate 200g, nickel chloride 45g, boric acid 30g;PH is 4.3, and temperature is 50 DEG C, and adopting pure nickel piece is anode; Be 3A/dm in current density2Lower plating 5min;
After plating completes, rinse well with clear water;
(7) alkaline non-cyanide high speed copper facing
Adopt electroplating bath shown in Fig. 1 to electroplate,
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises copper sulphate 50g, potassium hydroxide 20g, carboxylic acid potassiumSalt 40g, potassium tartrate, EDTA and natrium citricum in mass ratio 1:0.5:1 are composite, get 12.5g, poly-second twoAlcohol, 1.5:1 is composite in mass ratio for poly-two sulphur two ethane sulfonic acid sodium, gets 12g, cystine, asccharin and sulfo-sulphur0.5:1:1 is composite in mass ratio for acid sodium, gets 2.5g; PH is 8.0, and temperature is 55 DEG C, adopts high-purity copper billet to doFor anode; Be 3A/dm in current density2Lower plating 5min;
After plating completes, rinse well with clear water;
(8) passivation
Process conditions are: benzotriazole 5g/L, and temperature is 30 DEG C, the time is 2min;
First use hot water wash, then rinse well with clear water;
(9) heat treatment
In the nitrogen protection stove of 180 DEG C, toast 10min.
Prepared one side copper facing stainless steel band surface is observed, found surperficial inviolateness, rule without bubbling, nothingEtc. phenomenon.
By hundred lattice methods, the one side copper facing stainless steel band of preparation is tested, coating is without coming off.
The material making carries out neutral salt spray test, and 24 hours without rust spot.
Embodiment 3
Adopt the mode of horizontal transmission, electroplate one side on the lower, taking 304 stainless steel bands as base material, thickness is0.2mm, width is 200mm, adopts following technique, and it is processed.
(1) electrochemical deoiling
Process conditions are: in every liter of washings, comprise degreasing powder 80g, washing agent 5mL; Temperature is 55 DEG C,Time is 3min; Clean by hot water wash.
(2) electrolytic degreasing
Process conditions are: electrolyte: every liter of electrolyte comprises NaOH 60g, sodium carbonate 40g, tricresyl phosphateSodium 30g; Temperature is 65 DEG C, and current density is 3A/dm2；
First, using stainless steel band as negative electrode, inert electrode is anode, electrolytic degreasing 5min; Again by stainless steel bandAs anode, inert electrode is negative electrode, oil removing 5min; First clean by hot water wash, then rinse well with clear water;
(3) chemical activation
Process conditions are: the sulfuric acid of 10wt%, and temperature is 25 DEG C, soak time is 5min;
Rinse well with clear water;
(4) electrolysis, activation
Process conditions are: the hydrochloric acid that electrolyte is 15wt%, and temperature is 25 DEG C, using stainless steel band as negative electrode,Inert electrode is anode, is 2A/dm in current density2Lower electrolysis 6min,
After electrolysis completes, rinse well with clear water;
(5) nickel preplating
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises nickel chloride 80g, concentrated hydrochloric acid 180mL; PH is littleIn 1, temperature is 25 DEG C, adopts pure nickel piece as anode; Be 4A/dm in current density2Lower plating 1min;
After plating completes, rinse well with clear water;
(6) plate dark nickel
Process conditions are: electroplate liquid, and every liter of electroplate liquid comprises nickelous sulfate 240g, nickel chloride 35g, boric acid 40g;PH is 3, and temperature is 50 DEG C, and adopting pure nickel piece is anode; Be 3A/dm in current density2Lower plating 5min;
Rinse well with clear water;
(7) alkaline non-cyanide high speed copper facing
Adopt electroplating bath shown in Fig. 1 to electroplate,
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises copper sulphate 60g, potassium hydroxide 40g, carboxylic acid potassiumSalt 20g, biuret, glycerine and natrium citricum in mass ratio 2:0.5:1 are composite, get 45g, polyethylene glycol andPolymine sodium in mass ratio 1:1 is composite, gets 45g, and naphthalenedisulfonic acid, acetyl thiourea and sodium thiosulfate are pressedMass ratio 1:0.5:1 is composite, gets 6g; Temperature is 55 DEG C, and pH is 10, adopts high-purity copper billet as anode;Be 3A/dm in current density2Lower plating 5min;
After plating completes, rinse well with clear water;
(8) passivation
Process conditions are: benzotriazole 5g/L, and temperature is 30 DEG C, the time is 2min;
First use hot water wash, then rinse well with clear water;
(9) heat treatment
In the nitrogen protection stove of 180 DEG C, toast 10min.
Prepared one side copper facing stainless steel band surface is observed, found surperficial inviolateness, rule without bubbling, nothingEtc. phenomenon.
By hundred lattice methods, the one side copper facing stainless steel band of preparation is tested, coating is without coming off.
The material making carries out neutral salt spray test, and 24 hours without rust spot.
Embodiment 4
Taking 430 stainless steels as base material, adopt the mode one side rubberizing of vertical type transmission, another side is electroplated, and thickness is0.25mm, width is 120mm, adopts following technique, and it is processed.
(1) electrochemical deoiling
Process conditions are: in every liter of washings, comprise degreasing powder 60g, washing agent 5mL; Temperature is 45 DEG C,Time is 4min;
Clean by hot water wash;
(2) electrolytic degreasing
Process conditions are: electrolyte: every liter of electrolyte comprises NaOH 30g, sodium carbonate 30g, tricresyl phosphateSodium 30g; Temperature is 45 DEG C, and current density is 3A/dm2；
First, using stainless steel band as negative electrode, inert electrode is anode, electrolytic degreasing 6min; Again by stainless steel bandAs anode, inert electrode is negative electrode, oil removing 6min; Clean by hot water wash, then rinse well with clear water;
(3) chemical activation
Process conditions are: the sulfuric acid of 10wt%, and temperature is 25 DEG C, soak time is 5min;
Rinse well with clear water;
(4) electrolysis, activation
Process conditions are: the hydrochloric acid that electrolyte is 5wt%, and temperature is 25 DEG C, using stainless steel band as negative electrode,Inert electrode is anode; Be 3A/dm in current density2Lower electrolysis 7min;
After electrolysis completes, rinse well with clear water;
(5) nickel preplating
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises nickel chloride 200g, concentrated hydrochloric acid 180mL; PH is littleIn 1, temperature is 25 DEG C, adopts pure nickel piece as anode; Be 3A/dm in current density2Lower plating 0.8min;
After plating completes, rinse well with clear water.
(6) plate dark nickel
Process conditions are: electroplate liquid: every liter of electroplate liquid comprises nickelous sulfate 200g, nickel chloride 40g, boric acid 30g;PH is 4.3, and temperature is 50 DEG C, and adopting pure nickel piece is anode; Be 3A/dm in current density2Lower plating 3min;
Rinse well with clear water;
(7) alkaline non-cyanide high speed copper facing
Adopt electroplating bath shown in Fig. 1 to electroplate,
Process conditions are: electroplate liquid: electroplate liquid comprises copper sulphate 60g; Potassium hydroxide 30g; Carboxylic acid sylvite 30g;Biuret, HEDP and natrium citricum in mass ratio 2:1:1 are composite, get 18g, polyethylene glycol andPolymine sodium in mass ratio 1:1 is composite, gets 12.5g, cystine, acrylic thiocarbamide and sodium thiosulfate2:2:1 is composite in mass ratio, gets 4.5g; Temperature is 55 DEG C, and pH is 8.8, adopts high-purity copper billet as anode;Be 5A/dm in current density2Lower plating 4min;
After plating completes, rinse well with clear water;
(8) passivation
Process conditions are: benzotriazole 5g/L, and temperature is 30 DEG C, the time is 2min;
First use hot water wash, then rinse well with clear water;
(9) heat treatment
In the nitrogen protection stove of 180 DEG C, toast 10min.
Prepared one side copper facing stainless steel band surface is observed, find surface-brightening, inviolateness, without bubbling,Without phenomenons such as line.
With extra coarse degree tester, prepared one side copper facing stainless steel band surface is tested, result shows its tableThe coarse plating of face is Ra≤0.1 μ m.
By hundred lattice methods, the one side copper facing stainless steel band of preparation is tested, coating is without coming off.
The material making carries out neutral salt spray test, and 24 hours without rust spot.
Claims (8)
1. a wide cut stainless steel band one side copper coating, is characterized in that, by the pre-surfacing of substrate stainless steel bandAfter oil removing, activate; In the pre-surfacing of substrate stainless steel band activating, first plate nickel preplating, then plate dark nickel, finally existBe provided with copper facing in the electroplating bath of multistage rolling wall sealing device, described electroplating bath is two of transmission entrance and exit placeOn cell wall, at least two transmission transfer rollers have been installed in sealing respectively; When plating, alkaline nothing is housed in described electroplating bathCyanogen plating solution, adjusting current density is 2～8A/dm2, stainless steel band is established facing to described electroplating bath bottom land with preplatingThe electrode of putting, transmits from sealing between two parallel transmission transfer rollers, is parallel to bottom land through coating bath, carries out listFace copper facing; After the stainless steel band passivation after copper facing, drying, to obtain final product;
Wherein, every liter of alkaline non-cyanide plating solution comprises following component: copper sulphate 40～80g; Potassium hydroxide 10～50g;Carboxylic acid sylvite 10～50g; Complexing agent 6～60g; Dispersant 6～60g; Brightener 0.8～8g;
Described complexing agent be in potassium tartrate, biuret, glycerine, HEDP or EDTA at leastThe compound of two kinds and potassium citrate; In described complexing agent, the mass percent of potassium citrate is 25～50%;Described brightener is a kind of or several in naphthalenedisulfonic acid, asccharin, cystine, acetyl thiourea or acrylic thiocarbamideThe compound of kind and sodium thiosulfate;
In described brightener, the mass percent of sodium thiosulfate is 16～50%.
2. the method for claim 1, is characterized in that, described current density is 2～6A/dm2。
3. the method for claim 1, is characterized in that, described dispersant is polyethylene glycol, polyethyleneOne or more in imines, poly-two sulphur two ethane sulfonic acid sodium.
4. the method for claim 1, is characterized in that, described alkaline non-cyanide plating solution pH is 8.0～10.0.
5. the method for claim 1, is characterized in that, described copper facing temperature is 45～70 DEG C, the timeBe 1～20min.
6. the method for claim 1, is characterized in that, described activation is that substrate stainless steel band is first usedThe sulfuric acid of 2～20wt%, is at 15～35 DEG C in temperature, soaks 0.5～10min; Use again the hydrochloric acid of 2～20wt%,At 15～35 DEG C, using substrate stainless steel band as negative electrode, inert electrode is anode, in current density is0.1～5A/dm2Lower electrolysis 0.5～8min.
7. the method for claim 1, is characterized in that, described nickel preplating plating condition is: electroplate liquid:Every liter of electroplate liquid comprises the concentrated hydrochloric acid of 30～300g nickel chloride and 30～300mL; PH≤1, temperature is 15～35 DEG C,Anode is pure nickel piece; Be 0.5～5A/dm in current density2Lower plating 0.5～8min.
8. the method for claim 1, is characterized in that, the dark nickel plating of described plating condition is: electroplate liquid:Every liter of electroplate liquid comprises 180～300g nickelous sulfate, 15～50g nickel chloride and 15～50g boric acid; PH is 2.8～4.8,Temperature is 40～65 DEG C, and anode is pure nickel piece; Be 0.5～6A/dm in current density2Lower plating 0.5～10min.
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