CN104120462A - Method for carrying out cyanide-free cuprous brass electroplating on steel cord and method for passivating brass coating - Google Patents
Method for carrying out cyanide-free cuprous brass electroplating on steel cord and method for passivating brass coating Download PDFInfo
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- CN104120462A CN104120462A CN201410286791.9A CN201410286791A CN104120462A CN 104120462 A CN104120462 A CN 104120462A CN 201410286791 A CN201410286791 A CN 201410286791A CN 104120462 A CN104120462 A CN 104120462A
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Abstract
The invention relates to a method for carrying out cyanide-free cuprous brass electroplating on a steel cord and a method for passivating a brass coating and relates to a method for electroplating brass on the steel cord and a method for passivating the brass coating, aiming at the technical problems of difficult control over coating components, poor bonding force and poor corrosion resistance during the cyanide-free brass electroplating of the steel cord at present. The cyanide-free cuprous brass electroplating of the steel cord comprises the following steps of: preparing a cyanide-free cuprous brass electroplating solution; (2) pretreating the steel cord; (3) carrying out the cyanide-free cuprous brass electroplating on the steel cord. The brass coating with stable components and good bonding force is obtained by carrying out the cyanide-free cuprous brass electroplating on the steel cord. The method for passivating the brass electroplating comprises the following step of soaking the steel cord electroplated with the brass coating into a passivation solution for chemical passivation. The method for carrying out the cyanide-free cuprous brass electroplating on the steel cord and the method for passivating the brass coating can reduce the production cost of the steel cord and can be used for large-scale industrial production of the steel cord.
Description
Technical field
The invention belongs to steel cord surface modification field, relate to the electro-plating method of brass coating and the passivating method of this brass coating on steel cord.
Background technology
Steel cord matrix adopting high-quality high-carbon steel wire, can be used as the framework material of rubber, thereby can form with rubber the radial of excellent property, extends the work-ing life of tire, improves tire flexibility and anti-puncture ability.Because the relatively traditional bias tire of radial has more clear superiority, adopt at present steel cord to obtain wide application as radial reinforcement material, so the production of steel cord also become the gordian technique that Novel meridian tyre is manufactured.
In order to improve the bonding force of steel cord and rubber, the necessary brass plating in steel cord surface, and very high to the Composition Control requirement of brass coating, too high or too low zinc content is all unfavorable for the combination of steel cord and rubber.In steel cord plating brass technology, prussiate is electroplated and not only can be met the requirement that Coating composition is controlled, and low for the corrodibility of steel wire, can obtain the good brass coating of bonding force.Yet due to the hypertoxicity of prussiate, there is serious potential safety hazard in prussiate brass plating, is unfavorable for the environmental protection of production process.Along with the raising of people's environmental consciousness, the exploitation of cyanideless electro-plating brass technology becomes a vital task of steel cord production technology already.At present, for realize steel cord plating brass without cyaniding, generally all adopt without cyanogen alkali copper-sour copper thickening-obtain the technology of brass without cyanogen alkali zinc-thermodiffusion, obtain the rational brass coating of steel cord surface composition.Although this technical process can solve the control problem of Coating composition, but loaded down with trivial details flow process has not only increased production cost, and be also difficult for to obtain the good copper coating of bonding force in the first step in without the process of cyanogen alkali copper, likely cause the decline of follow-up whole binding force of cladding material.Find the strong complexing agent of the non-cyanogen of selectivity of cuprous ion or cupric ion, control separately the sedimentation potential of copper and avoid the violent corrosion to steel wire, obtain and form stable, the good brass coating of bonding force, thereby exploitation single stage method brass plating technology substitute system, will create huge society and economic benefit.
In addition for further strengthen steel cord solidity to corrosion and with the bonding force of rubber, the steel cord after plating brass adopts sexavalent chrome electrolytic passivation conventionally.Yet not only thickness distribution is inhomogeneous for the passivation layer that existing sexavalent chrome electrolytic passivation method obtains, be difficult to seal brass coating completely, and also also limited to the lifting degree of bonding force between steel cord and rubber.Therefore to be applicable to the passivation chemical passivation method even, simple to operate, that product performance are superior of brass coating significant in exploitation.
Summary of the invention
The present invention be to solve existing steel cord cyanideless electro-plating brass complex process, cost is higher, and the technical problem that Coating composition is unstable, solidity to corrosion is poor, and the passivating method of steel cord without the cuprous brass plating of cyanogen and brass coating is provided.
Steel cord of the present invention carries out according to following steps without the cuprous brass plating of cyanogen:
(1) without the preparation of the cuprous brass plating solution of cyanogen: a, the concentration that is 3 ~ 30g/L, antioxidant according to the concentration of Red copper oxide are that the concentration of 0.2 ~ 20.0g/L, cuprous complexing agent is that the concentration of 15 ~ 150g/L, auxiliary complex-former is that 10 ~ 100g/L takes respectively Red copper oxide, antioxidant, cuprous complexing agent and auxiliary complex-former; B, the antioxidant that step a is taken, cuprous complexing agent and auxiliary complex-former are dissolved in the acetic acid solution of 60mL/L successively, and heated and stirred obtains solution A to dissolving; C, the Red copper oxide taking in step a is joined in solution A, be stirred to dissolving, place and make solution B after 24 hours; D, the concentration that is 5 ~ 40g/L, sodium acetate according to acetic acid zinc concentration are that the concentration of 40 ~ 50g/L, leveling agent is that 0.005 ~ 2.500g/L takes respectively zinc acetate, sodium acetate and leveling agent; E, the zinc acetate taking in steps d, sodium acetate and leveling agent are joined and in solution B, be stirred to dissolving, after filtration, with acetic acid or ammoniacal liquor, adjust pH value to 3.0 ~ 6.5, join without the cuprous brass plating solution of cyanogen;
(2) steel cord pre-treatment: f, to adopt temperature be that the electrochemical deoiling liquid that 40 ~ 70 ℃, pH value are 9.0 ~ 13.0 carries out electrochemical deoiling 2 ~ 15 minutes to steel cord, the concentration that electrochemical deoiling liquid is 10 ~ 15g/L, water glass in the concentration of sodium hydroxide is that the concentration of 6 ~ 10g/L, sodium carbonate is that the concentration of 15 ~ 30g/L, OP-10 emulsifying agent is that the ratio of 1 ~ 5 g/L is formulated; G, by the steel cord through oil removing through twice tap water clean, after twice washed with de-ionized water, in temperature, be, in 25 ~ 40 ℃, the concentration expressed in percentage by volume sulphuric acid soln that is 5% ~ 10%, steel cord is carried out to pickling 0.5 ~ 5.0 minute, after the cleaning of twice tap water, twice washed with de-ionized water, complete the pre-treatment of steel cord again;
(3) steel cord without the cuprous brass plating of cyanogen: h, by step (1) preparation without the cuprous brass plating solution of cyanogen, be warming up to 25 ~ 80 ℃, adopt ruthenium titanium conformal anode, in cathode current density, be 0.6 ~ 4.0A/dm
2condition under steel cord is carried out to brass plating 2 ~ 30 minutes, then clean, after twice washed with de-ionized water, complete steel cord without the cuprous brass plating of cyanogen through twice tap water.
The a of step (1) and the antioxidant described in b are a kind of in uric acid, vitamins C, inferior sodium phosphate, Resorcinol, pyrocatechol or Resorcinol, described cuprous complexing agent is a kind of in thiosemicarbazide, tetramethyl thiourea, thiocarbamide or ethylene thiourea or wherein several combination, and described auxiliary complex-former is a kind of in Seignette salt, disodium ethylene diamine tetraacetate, trisodium citrate or Sunmorl N 60S; The d of step (1) and the leveling agent described in e are the combination of two kinds in ammonium molybdate, gelatin, peptone, stannous sulfate or nickelous acetate.
The Cu consuming in electroplating process without the cuprous brass plating solution of cyanogen
+and Zn
2+need regularly in plating solution, to add, replenishment method carries out according to following steps:
(1) take out a part of without the cuprous brass plating solution of cyanogen; (2) according to consuming Cu
+and Zn
2+total amount take Red copper oxide and zinc oxide, and in heating in the situation that, the Red copper oxide taking and zinc oxide are joined in cuprous brass plating solution, stirring until dissolve without cyanogen of taking-up; (3) by take out without the cuprous brass plating solution of cyanogen, add after refund coating bath.
The passivating method that is plated in the brass coating on steel cord carries out according to following steps:
(1) by the concentration of potassium bichromate, be that 3 ~ 40g/L, soluble tartrate na concn are that 5 ~ 20g/L takes potassium bichromate and Seignette salt, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 4.6 ~ 8.6, obtains chemical passivation liquid;
(2) by immerse temperature through the steel cord of brass plating, be in the chemical passivation liquid of step (1) preparation of 25 ~ 50 ℃ 2 ~ 15 minutes, then clean, after twice washed with de-ionized water, complete the passivation of brass coating through twice tap water.
Method of the present invention due in the cuprous brass plating solution without cyanogen, added can selective complexation cuprous ion cuprous complexing agent, when the steel cord to through pre-treatment carries out cyanideless electro-plating brass, can obtain on steel cord surface that Coating composition is stable, the good brass coating of bonding force, not only shorten production process, and reduced production cost.Steel cord surface brass coating after chemical passivation, can form complete uniform passive film in brass surfaces again, and its solidity to corrosion is increased dramatically.The present invention can solve the guardian technique problem of surperficial cyanideless electro-plating brass in the actual production of steel cord, for steel cord production, is significant.
Accompanying drawing explanation
Fig. 1 for test one in temperature, be that 50 ℃, current density are 2.0A/dm
2condition under through electroplating the electron scanning micrograph of gained brass coating after 10 minutes;
Fig. 2 for test one in temperature, be that 50 ℃, current density are 2.0A/dm
2condition under through electroplating (a) copper distribution plan of gained brass coating after 10 minutes and (b) zinc element distribution plan.
Embodiment
Embodiment one: the steel cord of present embodiment carries out according to the following steps without the cuprous brass plating of cyanogen:
(1) without the preparation of the cuprous brass plating solution of cyanogen: a, the concentration that is 3 ~ 30g/L, antioxidant according to the concentration of Red copper oxide are that the concentration of 0.2 ~ 20.0g/L, cuprous complexing agent is that the concentration of 15 ~ 150g/L, auxiliary complex-former is that 10 ~ 100g/L takes respectively Red copper oxide, antioxidant, cuprous complexing agent and auxiliary complex-former; B, the antioxidant that step a is taken, cuprous complexing agent and auxiliary complex-former are dissolved in the acetic acid solution of 60mL/L successively, and heated and stirred obtains solution A to dissolving; C, the Red copper oxide taking in step a is joined in solution A, be stirred to dissolving, place and make solution B after 24 hours; D, the concentration that is 5 ~ 40g/L, sodium acetate according to acetic acid zinc concentration are that the concentration of 40 ~ 50g/L, leveling agent is that 0.005 ~ 2.500g/L takes respectively zinc acetate, sodium acetate and leveling agent; E, the zinc acetate taking in steps d, sodium acetate and leveling agent are joined and in solution B, be stirred to dissolving, after filtration, with acetic acid or ammoniacal liquor, adjust pH value to 3.0 ~ 6.5, join without the cuprous brass plating solution of cyanogen;
(2) steel cord pre-treatment: f, to adopt temperature be that the electrochemical deoiling liquid that 40 ~ 70 ℃, pH value are 9.0 ~ 13.0 carries out electrochemical deoiling 2 ~ 15 minutes to steel cord, the concentration that electrochemical deoiling liquid is 10 ~ 15g/L, water glass in the concentration of sodium hydroxide is that the concentration of 6 ~ 10g/L, sodium carbonate is that the concentration of 15 ~ 30g/L, OP-10 emulsifying agent is that the ratio of 1 ~ 5 g/L is formulated; G, by the steel cord through oil removing through twice tap water clean, after twice washed with de-ionized water, in temperature, be, in 25 ~ 40 ℃, the concentration expressed in percentage by volume sulphuric acid soln that is 5% ~ 10%, steel cord is carried out to pickling 0.5 ~ 5.0 minute, after the cleaning of twice tap water, twice washed with de-ionized water, complete the pre-treatment of steel cord again;
(3) steel cord without the cuprous brass plating of cyanogen: h, by step (1) preparation without the cuprous brass plating solution of cyanogen, be warming up to 25 ~ 80 ℃, adopt ruthenium titanium conformal anode, in cathode current density, be 0.6 ~ 4.0A/dm
2condition under steel cord is carried out to brass plating 2 ~ 30 minutes, then clean, after twice washed with de-ionized water, complete steel cord without the cuprous brass plating of cyanogen through twice tap water.
The steel cord of present embodiment without the cuprous brass plating of cyanogen by the cuprous brass plating solution without cyanogen, added can selective complexation cuprous ion cuprous complexing agent, when the steel cord to through pre-treatment carries out cyanideless electro-plating brass, can obtain on steel cord surface that Coating composition is stable, the good brass coating of bonding force, not only shorten production process, and reduced production cost.Present embodiment can solve the guardian technique problem that in the actual production of steel cord, surperficial cyanideless electro-plating brass coating composition is wayward, binding force of cladding material is poor, for steel cord production, is significant.
Embodiment two: present embodiment is different from embodiment one is that a of step (1) and the antioxidant described in b are a kind of in uric acid, vitamins C, inferior sodium phosphate, Resorcinol, pyrocatechol or Resorcinol, and concentration is 0.5 ~ 15.0g/L.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is that a of step (1) and the cuprous complexing agent described in b are a kind of in thiosemicarbazide, tetramethyl thiourea, thiocarbamide or ethylene thiourea or wherein several combination, and concentration is 18 ~ 145g/L.Other is identical with embodiment one or two.
When the cuprous complexing agent of present embodiment is composition, various cuprous complexing agents are by any combination.
Embodiment four: present embodiment is different from one of embodiment one to three is that a of step (1) and the auxiliary complex-former described in b are a kind of in Seignette salt, disodium ethylene diamine tetraacetate, trisodium citrate or Sunmorl N 60S, and concentration is 15 ~ 90g/L.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four be the d of step (1) and the leveling agent described in e be in ammonium molybdate, gelatin, peptone, stannous sulfate or nickelous acetate two kinds by the combination of any ratio, concentration is 0.01 ~ 1.50g/L.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five is to take in the f of step (2) in the electrochemical deoiling liquid that 45 ~ 65 ℃, pH value are 9.5 ~ 12.5, steel cord to be carried out to electrochemical deoiling 3 ~ 12 minutes in temperature, the concentration that electrochemical deoiling liquid is 12 ~ 14g/L, water glass in the concentration of sodium hydroxide is that the concentration of 7 ~ 9g/L, sodium carbonate is that the concentration of 16 ~ 25g/L, OP-10 emulsifying agent is that the ratio of 2 ~ 4 g/L is formulated.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six be in the h in step (3) by step (1) preparation without the cuprous brass plating solution of cyanogen, to be warming up to temperature be 30 ~ 70 ℃, adopting ruthenium titanium conformal anode, is 0.8 ~ 3.0A/dm in cathode current density
2condition under steel cord is carried out to brass plating 2 ~ 30 minutes.Other is identical with one of embodiment one to six.
Embodiment eight: that present embodiment is different from one of embodiment one to seven is the described Cu consuming in electroplating process without the cuprous brass plating solution of cyanogen
+and Zn
2+need regularly in plating solution, to add, replenishment method carries out according to following steps:
(1) take out a part of without the cuprous brass plating solution of cyanogen; (2) according to consuming Cu
+and Zn
2+total amount take Red copper oxide and zinc oxide, and in heating in the situation that, the Red copper oxide taking and zinc oxide are joined in cuprous brass plating solution, stirring until dissolve without cyanogen of taking-up; (3) by take out without the cuprous brass plating solution of cyanogen, add after refund coating bath.
Other is identical with one of embodiment one to seven.
Embodiment nine: the passivating method that is plated in the brass coating on steel cord described in embodiment one carries out according to the following steps:
(1) by the concentration of potassium bichromate, be that 3 ~ 40g/L, soluble tartrate na concn are that 5 ~ 20g/L takes potassium bichromate and Seignette salt, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 4.6 ~ 8.6, obtains chemical passivation liquid;
(2) by immerse temperature through the steel cord of brass plating, be in the chemical passivation liquid of step (1) preparation of 25 ~ 50 ℃ 2 ~ 15 minutes, then clean, after twice washed with de-ionized water, complete the passivation of brass coating through twice tap water.
Present embodiment adopts after chemical passivation the brass coating being plated on steel cord, can form complete uniform passive film in brass surfaces, and its solidity to corrosion is increased dramatically.
Embodiment ten: present embodiment is different from embodiment nine is in step (1) to be that 5 ~ 35g/L, soluble tartrate na concn are that 6 ~ 18g/L takes potassium bichromate and Seignette salt by the concentration of potassium bichromate, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 4.8 ~ 8.0, obtains chemical passivation liquid.Other is identical with embodiment nine.
Embodiment 11: present embodiment is different from embodiment nine or ten is that in step (2), the steel cord through brass plating to be immersed to temperature be in the chemical passivation liquid of step (1) preparation of 30 ~ 45 ℃ 3 ~ 12 minutes, after the cleaning of twice tap water, twice washed with de-ionized water, complete the passivation of brass coating again.Other is identical with embodiment nine or ten.
With following verification experimental verification beneficial effect of the present invention:
Test one: the steel cord of this test carries out according to the following steps without the cuprous brass plating of cyanogen:
(1) without the preparation of the cuprous brass plating solution of cyanogen: a, the concentration that is 20g/L, Resorcinol according to the concentration of Red copper oxide are that the concentration of 10.0g/L, thiocarbamide is that the concentration of 100g/L, ethylene thiourea is that the concentration of 20g/L, Seignette salt is that 75g/L takes respectively Red copper oxide, Resorcinol, thiocarbamide, ethylene thiourea and Seignette salt; B, the Resorcinol that step a is taken, thiocarbamide, ethylene thiourea and Seignette salt are dissolved in the acetic acid solution of 60mL/L successively, and heated and stirred obtains solution A to dissolving; C, the Red copper oxide taking in step a is joined in solution A, be stirred to dissolving, place and make solution B after 24 hours; D, the concentration that is 25g/L, sodium acetate according to acetic acid zinc concentration are that the concentration of 45g/L, gelatin is that the concentration of 0.10g/L, nickelous acetate is that 0.25g/L takes respectively zinc acetate, sodium acetate, gelatin and nickelous acetate; E, the zinc acetate taking in steps d, sodium acetate, gelatin and nickelous acetate are joined and in solution B, be stirred to dissolving, after filtration, with acetic acid or ammoniacal liquor, adjust pH value to 3.5, join without the cuprous brass plating solution of cyanogen;
(2) steel cord pre-treatment: f, in temperature, be, in 60 ℃, the pH value electrochemical deoiling liquid that is 10.5, steel cord is carried out to electrochemical deoiling 5 minutes, the concentration that electrochemical deoiling liquid is 13g/L, water glass in the concentration of sodium hydroxide is that the concentration of 8g/L, sodium carbonate is that the concentration of 20g/L, OP-10 emulsifying agent is that the ratio of 3 g/L is formulated; G, by the steel cord through oil removing through twice tap water clean, after twice washed with de-ionized water, in temperature, be, in 30 ℃, the concentration expressed in percentage by volume sulphuric acid soln that is 8%, steel cord is carried out to pickling 1.0 minutes, after the cleaning of twice tap water, twice washed with de-ionized water, complete the pre-treatment of steel cord again;
(3) steel cord without the cuprous brass plating of cyanogen: h, by step (1) preparation without the cuprous brass plating solution of cyanogen, be warming up to 50 ℃, adopt ruthenium titanium conformal anode, in cathode current density, be 2.0A/dm
2condition under steel cord is carried out to brass plating 10 minutes, then clean, after twice washed with de-ionized water, complete steel cord without the cuprous brass plating of cyanogen through twice tap water.
This test obtains brass coating electron scanning micrograph on steel cord surface as shown in Figure 1, as can be seen from Figure 1, by obtaining the careful brass coating of homogeneous on steel cord surface without the cuprous brass plating of cyanogen.
This test obtains the copper distribution plan of brass coating and zinc element distribution plan as shown in Figure 2 on steel cord surface, as can be seen from Figure 2, copper and zinc element are evenly distributed in gained brass coating, and analytical results shows that in coating, copper content is 69.6%, zinc element content is 30.4%, has reached the requirement of steel cord surface brass coating.
The Cu consuming in electroplating process without the cuprous brass plating solution of cyanogen
+and Zn
2+need regularly in plating solution, to add, replenishment method carries out according to following steps:
(1) take out a part of without the cuprous brass plating solution of cyanogen; (2) according to consuming Cu
+and Zn
2+total amount take Red copper oxide and zinc oxide, and in heating in the situation that, the Red copper oxide taking and zinc oxide are joined in cuprous brass plating solution, stirring until dissolve without cyanogen of taking-up; (3) by take out without the cuprous brass plating solution of cyanogen, add after refund coating bath.
The above-mentioned passivating method that is plated in the brass coating on steel cord carries out according to the following steps:
(1) by the concentration of potassium bichromate, be that 25g/L, soluble tartrate na concn are that 16g/L takes potassium bichromate and Seignette salt, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 6.0, obtains chemical passivation liquid;
(2) by immerse temperature through the steel cord of brass plating, be in the chemical passivation liquid of step (1) preparation of 40 ℃ 5 minutes, then clean, after twice washed with de-ionized water, complete the passivation of brass coating through twice tap water.
Chemical purification process through above-mentioned, obtains passive film on brass coating surface, and according to Electrochemical results, after passivation, the erosion rate of coating is 1/162.6 before passivation.
Test two: this test and the difference of testing one be steel cord without in the cuprous brass plating of cyanogen without the preparation of the cuprous brass plating solution of cyanogen: a, the concentration that is 15g/L, Resorcinol according to the concentration of Red copper oxide are that the concentration of 10.0g/L, thiocarbamide is that the concentration of 80g/L, ethylene thiourea is that the concentration of 10g/L, Seignette salt is that 60g/L takes respectively Red copper oxide, Resorcinol, thiocarbamide, ethylene thiourea and Seignette salt; B, the Resorcinol that step a is taken, thiocarbamide, ethylene thiourea and Seignette salt are dissolved in the acetic acid solution of 60mL/L successively, and heated and stirred obtains solution A to dissolving; C, the Red copper oxide taking in step a is joined in solution A, be stirred to dissolving, place and make solution B after 24 hours; D, the concentration that is 20g/L, sodium acetate according to acetic acid zinc concentration are that the concentration of 40g/L, gelatin is that the concentration of 0.10g/L, nickelous acetate is that 0.20g/L takes respectively zinc acetate, sodium acetate, gelatin and nickelous acetate; E, the zinc acetate taking in steps d, sodium acetate, gelatin and nickelous acetate are joined and in solution B, be stirred to dissolving, after filtration, with acetic acid or ammoniacal liquor, adjust pH value to 3.5, join without the cuprous brass plating solution of cyanogen.Other step is identical with test one with parameter.
This test copper content in steel cord surface obtains brass coating is 68.5%, and zinc element content is 31.5%, has reached the requirement of steel cord surface brass coating.
Test three: this test and the difference of testing one be steel cord without in the cuprous brass plating of cyanogen without the preparation of the cuprous brass plating solution of cyanogen: a, the concentration that is 18g/L, Resorcinol according to the concentration of Red copper oxide are that the concentration of 8.0g/L, thiocarbamide is that the concentration of 80g/L, thiosemicarbazide is that the concentration of 35g/L, Sunmorl N 60S is that 60g/L takes respectively Red copper oxide, Resorcinol, thiocarbamide, thiosemicarbazide and Sunmorl N 60S; B, the Resorcinol that step a is taken, thiocarbamide, thiosemicarbazide and Sunmorl N 60S are dissolved in the acetic acid solution of 60mL/L successively, and heated and stirred obtains solution A to dissolving; C, the Red copper oxide taking in step a is joined in solution A, be stirred to dissolving, place and make solution B after 24 hours; D, the concentration that is 22g/L, sodium acetate according to acetic acid zinc concentration are that the concentration of 40g/L, peptone is that the concentration of 0.1g/L, stannous sulfate is that 0.25g/L takes respectively zinc acetate, sodium acetate, peptone and stannous sulfate; E, the zinc acetate taking in steps d, sodium acetate, peptone and stannous sulfate are joined and in solution B, be stirred to dissolving, after filtration, with acetic acid or ammoniacal liquor, adjust pH value to 4.0, join without the cuprous brass plating solution of cyanogen.Other step is identical with test one with parameter.
This test copper content in steel cord surface obtains brass coating is 69.2%, and zinc element content is 30.8%, has reached the requirement of steel cord surface brass coating.
Test four: what this test was different from test one is that the passivating method that is plated in the brass coating on steel cord carries out according to the following steps:
(1) by the concentration of potassium bichromate, be that 15g/L, soluble tartrate na concn are that 10g/L takes potassium bichromate and Seignette salt, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 5.6, obtains chemical passivation liquid;
(2) by immerse temperature through the steel cord of brass plating, be in the chemical passivation liquid of step (1) preparation of 50 ℃ 6 minutes, then clean, after twice washed with de-ionized water, complete the passivation of brass coating through twice tap water.
Other step is identical with test one with parameter.
Chemical purification process through above-mentioned, obtains passive film on brass coating surface, and according to Electrochemical results, after passivation, the erosion rate of coating is 1/126.8 before passivation.
Claims (10)
1. steel cord, without the cuprous brass plating of cyanogen, is characterized in that steel cord carries out according to the following steps without the cuprous brass plating of cyanogen:
(1) without the preparation of the cuprous brass plating solution of cyanogen: a, the concentration that is 3 ~ 30g/L, antioxidant according to the concentration of Red copper oxide are that the concentration of 0.2 ~ 20.0g/L, cuprous complexing agent is that the concentration of 15 ~ 150g/L, auxiliary complex-former is that 10 ~ 100g/L takes respectively Red copper oxide, antioxidant, cuprous complexing agent and auxiliary complex-former; B, the antioxidant that step a is taken, cuprous complexing agent and auxiliary complex-former are dissolved in the acetic acid solution of 60mL/L successively, and heated and stirred obtains solution A to dissolving; C, the Red copper oxide taking in step a is joined in solution A, be stirred to dissolving, place and make solution B after 24 hours; D, the concentration that is 5 ~ 40g/L, sodium acetate according to acetic acid zinc concentration are that the concentration of 40 ~ 50g/L, leveling agent is that 0.005 ~ 2.500g/L takes respectively zinc acetate, sodium acetate and leveling agent; E, the zinc acetate taking in steps d, sodium acetate and leveling agent are joined and in solution B, be stirred to dissolving, after filtration, with acetic acid or ammoniacal liquor, adjust pH value to 3.0 ~ 6.5, join without the cuprous brass plating solution of cyanogen;
(2) steel cord pre-treatment: f, to adopt temperature be that the electrochemical deoiling liquid that 40 ~ 70 ℃, pH value are 9.0 ~ 13.0 carries out electrochemical deoiling 2 ~ 15 minutes to steel cord, the concentration that electrochemical deoiling liquid is 10 ~ 15g/L, water glass in the concentration of sodium hydroxide is that the concentration of 6 ~ 10g/L, sodium carbonate is that the concentration of 15 ~ 30g/L, OP-10 emulsifying agent is that the ratio of 1 ~ 5 g/L is formulated; G, by the steel cord through oil removing through twice tap water clean, after twice washed with de-ionized water, in temperature, be, in 25 ~ 40 ℃, the concentration expressed in percentage by volume sulphuric acid soln that is 5% ~ 10%, steel cord is carried out to pickling 0.5 ~ 5.0 minute, after the cleaning of twice tap water, twice washed with de-ionized water, complete the pre-treatment of steel cord again;
(3) steel cord without the cuprous brass plating of cyanogen: h, by step (1) preparation without the cuprous brass plating solution of cyanogen, be warming up to 25 ~ 80 ℃, adopt ruthenium titanium conformal anode, in cathode current density, be 0.6 ~ 4.0A/dm
2condition under steel cord is carried out to brass plating 2 ~ 30 minutes, then clean, after twice washed with de-ionized water, complete steel cord without the cuprous brass plating of cyanogen through twice tap water.
2. steel cord according to claim 1 is without the cuprous brass plating of cyanogen, it is characterized in that a of step (1) and the antioxidant described in b are a kind of in uric acid, vitamins C, inferior sodium phosphate, Resorcinol, pyrocatechol or Resorcinol, concentration is 0.5 ~ 15.0g/L.
3. steel cord according to claim 1 is without the cuprous brass plating of cyanogen, it is characterized in that a of step (1) and the cuprous complexing agent described in b are a kind of in thiosemicarbazide, tetramethyl thiourea, thiocarbamide or ethylene thiourea or wherein several combination, concentration is 18 ~ 145g/L.
4. steel cord according to claim 1 is without the cuprous brass plating of cyanogen, it is characterized in that a of step (1) and the auxiliary complex-former described in b are a kind of in Seignette salt, disodium ethylene diamine tetraacetate, trisodium citrate or Sunmorl N 60S, concentration is 15 ~ 90g/L.
5. steel cord according to claim 1 is without the cuprous brass plating of cyanogen, it is characterized in that the d of step (1) and the leveling agent described in e are the combination of two kinds in ammonium molybdate, gelatin, peptone, stannous sulfate or nickelous acetate, and concentration is 0.01 ~ 1.50g/L.
6. steel cord according to claim 1 is without the cuprous brass plating of cyanogen, it is characterized in that take in the f of step (2) in the electrochemical deoiling liquid that 45 ~ 65 ℃, pH value are 9.5 ~ 12.5, steel cord being carried out to electrochemical deoiling 3 ~ 12 minutes in temperature, the concentration that electrochemical deoiling liquid is 12 ~ 14g/L, water glass in the concentration of sodium hydroxide is that the concentration of 7 ~ 9g/L, sodium carbonate is that the concentration of 16 ~ 25g/L, OP-10 emulsifying agent is that the ratio of 2 ~ 4 g/L is formulated.
7. steel cord according to claim 1 is without the cuprous brass plating of cyanogen, it is characterized in that in the h in step (3) by step (1) preparation without the cuprous brass plating solution of cyanogen, to be warming up to temperature be 30 ~ 70 ℃, adopting ruthenium titanium conformal anode, is 0.8 ~ 3.0A/dm in cathode current density
2condition under steel cord is carried out to brass plating 2 ~ 30 minutes.
According to the steel cord described in aforementioned any one claim without the cuprous brass plating of cyanogen, it is characterized in that the described Cu consuming without the cuprous brass plating solution of cyanogen in electroplating process
+and Zn
2+need regularly in plating solution, to add, replenishment method carries out according to following steps:
(1) take out a part of without the cuprous brass plating solution of cyanogen; (2) according to consuming Cu
+and Zn
2+total amount take Red copper oxide and zinc oxide, and in heating in the situation that, the Red copper oxide taking and zinc oxide are joined in cuprous brass plating solution, stirring until dissolve without cyanogen of taking-up; (3) by take out without the cuprous brass plating solution of cyanogen, add after refund coating bath.
9. according to the passivating method that is plated in the brass coating on steel cord described in aforementioned any one claim, it is characterized in that the passivating method of brass coating carries out in accordance with the following methods:
(1) by the concentration of potassium bichromate, be that 3 ~ 40g/L, soluble tartrate na concn are that 5 ~ 20g/L takes potassium bichromate and Seignette salt, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 4.6 ~ 8.6, obtains chemical passivation liquid;
(2) by immerse temperature through the steel cord of brass plating, be in the chemical passivation liquid of step (1) preparation of 25 ~ 50 ℃ 2 ~ 15 minutes, then clean, after twice washed with de-ionized water, complete the passivation of brass coating through twice tap water.
10. the passivating method that is plated in the brass coating on steel cord according to claim 9, it is characterized in that in step (1) being that 5 ~ 35g/L, soluble tartrate na concn are that 6 ~ 18g/L takes potassium bichromate and Seignette salt by the concentration of potassium bichromate, be added to the water and be stirred to dissolving, then adopting the pH value of sulfuric acid or potassium hydroxide regulator solution is 4.8 ~ 8.0, obtains chemical passivation liquid; In step (2), by immerse temperature through the steel cord of brass plating, be in the chemical passivation liquid of step (1) preparation of 30 ~ 45 ℃ 3 ~ 12 minutes, then clean, after twice washed with de-ionized water, complete the passivation of brass coating through twice tap water.
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| CN201410286791.9A CN104120462B (en) | 2014-06-25 | 2014-06-25 | Steel cord is without the cuprous brass plating of cyanogen and the passivating method of brass coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108149285A (en) * | 2017-12-28 | 2018-06-12 | 广东达志环保科技股份有限公司 | Non-cyanide plating solution for copper-plating used and electro-plating method |
| CN109706487A (en) * | 2017-10-26 | 2019-05-03 | 丹阳市金长汽车部件有限公司 | A kind of anti-oxidant electroplate liquid of copper facing |
| CN111763965A (en) * | 2020-06-28 | 2020-10-13 | 贵州新华生化科技发展有限公司 | Reagent peptone for electroplating and preparation method thereof |
| CN111979568A (en) * | 2020-07-09 | 2020-11-24 | 江苏兴达钢帘线股份有限公司 | One-step method electroplating brass steel wire plating post-treatment method |
| CN114855156A (en) * | 2022-05-09 | 2022-08-05 | 如皋市凯源电器设备有限公司 | Preparation process of corrosion-resistant conductive strip |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027162A (en) * | 2008-05-12 | 2011-04-20 | 株式会社普利司通 | Copper-zinc alloy electroplating bath and plating method using same |
| JP2011174100A (en) * | 2010-02-23 | 2011-09-08 | Osaka Municipal Technical Research Institute | Copper-zinc alloy electroplating liquid |
| JP2011179152A (en) * | 2010-03-03 | 2011-09-15 | Bridgestone Corp | Method for producing rubber-reinforcing wire, rubber-reinforcing wire and rubber-reinforcing wire-rubber composite material using the same |
| CN102341530A (en) * | 2009-03-04 | 2012-02-01 | 株式会社普利司通 | Copper-zinc alloy electroplating bath and method of plating using same |
-
2014
- 2014-06-25 CN CN201410286791.9A patent/CN104120462B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027162A (en) * | 2008-05-12 | 2011-04-20 | 株式会社普利司通 | Copper-zinc alloy electroplating bath and plating method using same |
| CN102341530A (en) * | 2009-03-04 | 2012-02-01 | 株式会社普利司通 | Copper-zinc alloy electroplating bath and method of plating using same |
| JP2011174100A (en) * | 2010-02-23 | 2011-09-08 | Osaka Municipal Technical Research Institute | Copper-zinc alloy electroplating liquid |
| JP2011179152A (en) * | 2010-03-03 | 2011-09-15 | Bridgestone Corp | Method for producing rubber-reinforcing wire, rubber-reinforcing wire and rubber-reinforcing wire-rubber composite material using the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109706487A (en) * | 2017-10-26 | 2019-05-03 | 丹阳市金长汽车部件有限公司 | A kind of anti-oxidant electroplate liquid of copper facing |
| CN108149285A (en) * | 2017-12-28 | 2018-06-12 | 广东达志环保科技股份有限公司 | Non-cyanide plating solution for copper-plating used and electro-plating method |
| CN111763965A (en) * | 2020-06-28 | 2020-10-13 | 贵州新华生化科技发展有限公司 | Reagent peptone for electroplating and preparation method thereof |
| CN111979568A (en) * | 2020-07-09 | 2020-11-24 | 江苏兴达钢帘线股份有限公司 | One-step method electroplating brass steel wire plating post-treatment method |
| CN111979568B (en) * | 2020-07-09 | 2022-08-12 | 江苏兴达钢帘线股份有限公司 | One-step method electroplating brass steel wire plating post-treatment method |
| CN114855156A (en) * | 2022-05-09 | 2022-08-05 | 如皋市凯源电器设备有限公司 | Preparation process of corrosion-resistant conductive strip |
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