CN104120462B - Steel cord is without the cuprous brass plating of cyanogen and the passivating method of brass coating - Google Patents
Steel cord is without the cuprous brass plating of cyanogen and the passivating method of brass coating Download PDFInfo
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Abstract
Steel cord, without the cuprous brass plating of cyanogen and the passivating method of brass coating, the present invention relates to method and the passivating method of brass coating of steel cord plating pyrite.When the present invention is to solve current steel cord cyanideless electro-plating pyrite, Coating composition is difficult to control to, adhesion is poor, the technical problem of corrosion resistance difference.Steel cord is without the cuprous brass plating of cyanogen: (1) is without the preparation of cyanogen cuprous brass plating solution；(2) steel cord pre-treatment；(3) steel cord is without the cuprous brass plating of cyanogen.Steel cord is carried out without the cuprous brass plating of cyanogen, obtain the brass coating that stable components, adhesion are good.The passivating method of brass coating: the steel cord being coated with brass coating is immersed chemical passivation in passivating dip.Steel cord can reduce the production cost of steel cord without the passivating method of the cuprous brass plating of cyanogen and brass coating, can be used for the large-scale industrial production of steel cord.
Description
Technical field
The invention belongs to steel cord surface modification field, relate to the electro-plating method of brass coating on steel cord and the passivating method of this brass coating.
Background technology
Steel cord matrix uses high-quality high-carbon steel wire, such that it is able to form the radial of function admirable with rubber, can extend the service life of tire as the framework material of rubber, improve tire flexibility and puncture resistant ability.Owing to the bias tire that radial is relatively conventional has more clear superiority, using steel cord to obtain wide application as radial reinforcement material at present, therefore the production of steel cord also becomes the key technology that Novel meridian tyre manufactures.
In order to improve the adhesion of steel cord and rubber, the necessary brass plating of steel cord surface, and the Composition Control of brass coating is required the highest, too high or too low Zn content is all unfavorable for the combination of steel cord and rubber.In steel cord plating pyrite technology, cyanide plating is possible not only to meet the requirement that Coating composition controls, and the corrosivity for steel wire is low, it is possible to obtain the brass coating that adhesion is good.But, due to the hypertoxicity of cyanide, there is serious potential safety hazard in cyanide 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 pyrite technology becomes a vital task of steel cord production technology already.At present, in order to realize steel cord plating pyrite without cyaniding, the most all use and thicken the technology without cyanogen alkali zinc thermal diffusion acquisition pyrite without cyanogen alkali copper acid copper, obtain the steel rational brass coating of cord surface composition.Although this technological process can solve the control problem of Coating composition, but loaded down with trivial details flow process not only adds production cost, and be not easy to obtain the copper coating that adhesion is good during the first step is without cyanogen alkali copper, it is possible to cause the decline of follow-up whole binding force of cladding material.Find cuprous ion or the selectivity strong chelating agent of non-cyanogen of copper ion, individually control the sedimentation potential of copper and avoid the violent corrosion to steel wire, obtain the brass coating that composition is stable, adhesion is good, thus develop one-step method brass plating technical substitution hydride systems, it will create huge Social and economic benef@.
In addition to further enhance steel cord corrosion resistance and with the adhesion of rubber, the steel cord after plating pyrite generally uses Cr VI electrolytic passivation.But, the passivation layer not only thickness distribution that existing Cr VI electrolytic passivation method obtains is uneven, is difficult to completely enclosed brass coating, and the most limited to the lifting degree of adhesion between steel cord and rubber.Therefore exploitation be applicable to brass coating be passivated chemical passivation method uniform, simple to operate, that properties of product are superior significant.
Summary of the invention
The present invention is to solve existing steel cord cyanideless electro-plating pyrite complex process, relatively costly, and Coating composition is unstable, the technical problem of corrosion resistance difference, and provide steel cord without the cuprous brass plating of cyanogen and the passivating method of brass coating.
The steel cord of the present invention follows the steps below without the cuprous brass plating of cyanogen:
(1) without the preparation of cyanogen cuprous brass plating solution: a, according to the concentration of Red copper oxide be 3 ~ 30g/L, the concentration of antioxidant be 0.2 ~ 20.0g/L, the concentration of cuprous chelating agent be 15 ~ 150g/L, the concentration of auxiliary complex-former be that 10 ~ 100g/L weighs Red copper oxide, antioxidant, cuprous chelating agent and auxiliary complex-former respectively；B, antioxidant step a weighed, cuprous chelating 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 weighed in step a is joined in solution A, stirring to dissolving, obtained solution B after placing 24 hours；D, be 5 ~ 40g/L according to acetic acid zinc concentration, the concentration of sodium acetate be 40 ~ 50g/L, the concentration of leveling agent be that 0.005 ~ 2.500g/L weighs zinc acetate, sodium acetate and leveling agent respectively；E, the zinc acetate weighed in step d, sodium acetate and leveling agent are joined in solution B stirring to dissolving, adjust pH value to 3.0 ~ 6.5 with acetic acid or ammonia after filtration, join without cyanogen cuprous brass plating solution；
(2) steel cord pre-treatment: f, to use temperature be 40 ~ 70 DEG C, pH value is 9.0 ~ 13.0 electrochemical deoiling liquid carry out electrochemical deoiling 2 ~ 15 minutes to steel cord, electrochemical deoiling liquid by the concentration of sodium hydroxide be 10 ~ 15g/L, the concentration of sodium silicate be 6 ~ 10g/L, the concentration of sodium carbonate be 15 ~ 30g/L, the proportions that concentration is 1 ~ 5 g/L of OP-10 emulsifying agent forms；G, by through oil removing steel cord through twice tap water clean, twice deionized water clean after, temperature be 25 ~ 40 DEG C, concentration expressed in percentage by volume be 5% ~ 10% sulfuric acid solution in steel cord is carried out pickling 0.5 ~ 5.0 minute, again after the cleaning of twice tap water, twice deionized water clean, complete the pre-treatment of steel cord；
(3) steel cord without the cuprous brass plating of cyanogen: h, step (1) is prepared be warming up to 25 ~ 80 DEG C without cyanogen cuprous brass plating solution, use ruthenium titanium conformal anode, be 0.6 ~ 4.0A/dm in cathode-current density2Under conditions of steel cord is carried out brass plating 2 ~ 30 minutes, then through twice tap water clean, twice deionized water clean after, complete steel cord without the cuprous brass plating of cyanogen.
Antioxidant described in a and b of step (1) is the one in uric acid, vitamin C, sodium hypophosphite, hydroquinone, catechol or resorcinol, described cuprous chelating agent is a kind of or the most several combination in thiosemicarbazide, tetramethyl thiourea, thiourea or ethylene thiourea, and described auxiliary complex-former is the one in sodium potassium tartrate tetrahydrate, disodiumedetate, trisodium citrate or sodium gluconate；Leveling agent described in d and e of step (1) is the combination of two kinds in ammonium molybdate, gelatin, peptone, stannous sulfate or nickel acetate.
The Cu consumed in electroplating process without cyanogen cuprous brass plating solution+And Zn2+Needing periodically to add in plating solution, replenishment method follows the steps below:
(1) take out a part without cyanogen cuprous brass plating solution；(2) according to consuming Cu+And Zn2+Total amount weigh Red copper oxide and zinc oxide, and in case of heating the Red copper oxide weighed and zinc oxide are joined taking-up without in cyanogen cuprous brass plating solution, stirring is until dissolving；(3) by take out add without cyanogen cuprous brass plating solution after refund coating bath.
The passivating method being plated in the brass coating on steel cord follows the steps below:
(1) by the concentration of potassium dichromate be 3 ~ 40g/L, Soluble tartar. na concn be that 5 ~ 20g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, it is added to the water stirring to dissolving, then the pH value using sulphuric acid or potassium hydroxide regulation solution is 4.6 ~ 8.6, obtains chemical passivation liquid；
(2) it is in the chemical passivation liquid prepared of the step (1) of 25 ~ 50 DEG C 2 ~ 15 minutes that the steel cord through brass plating immerses temperature, then cleans through twice tap water, after twice deionized water cleans, completes the passivation of brass coating.
The method of the present invention can be with the cuprous chelating agent of selective complexation cuprous ion owing to the addition of in without cyanogen cuprous brass plating solution, when the steel cord through pre-treatment is carried out cyanideless electro-plating pyrite, the brass coating that Coating composition is stable, adhesion is good can be obtained at steel cord surface, not only shorten production process, and reduce production cost.Steel cord surface brass coating, again after chemical passivation, can form complete uniform passivating film in brass surfaces so that it is corrosion resistance is increased dramatically.The present invention can solve the crucial technical problem of surface cyanideless electro-plating pyrite in steel cord actual production, is significant for steel cord manufacturing industry.
Accompanying drawing explanation
Fig. 1 for test one temperature be 50 DEG C, electric current density be 2.0A/dm2Under conditions of after plating 10 minutes the electron scanning micrograph of gained brass coating；
Fig. 2 for test one temperature be 50 DEG C, electric current density be 2.0A/dm2Under conditions of after plating 10 minutes (a) copper scattergram of gained brass coating and (b) zinc element scattergram.
Detailed description of the invention
Detailed description of the invention one: the steel cord of present embodiment sequentially includes the following steps: without the cuprous brass plating of cyanogen
(1) without the preparation of cyanogen cuprous brass plating solution: a, according to the concentration of Red copper oxide be 3 ~ 30g/L, the concentration of antioxidant be 0.2 ~ 20.0g/L, the concentration of cuprous chelating agent be 15 ~ 150g/L, the concentration of auxiliary complex-former be that 10 ~ 100g/L weighs Red copper oxide, antioxidant, cuprous chelating agent and auxiliary complex-former respectively；B, antioxidant step a weighed, cuprous chelating 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 weighed in step a is joined in solution A, stirring to dissolving, obtained solution B after placing 24 hours；D, be 5 ~ 40g/L according to acetic acid zinc concentration, the concentration of sodium acetate be 40 ~ 50g/L, the concentration of leveling agent be that 0.005 ~ 2.500g/L weighs zinc acetate, sodium acetate and leveling agent respectively；E, the zinc acetate weighed in step d, sodium acetate and leveling agent are joined in solution B stirring to dissolving, adjust pH value to 3.0 ~ 6.5 with acetic acid or ammonia after filtration, join without cyanogen cuprous brass plating solution；
(2) steel cord pre-treatment: f, to use temperature be 40 ~ 70 DEG C, pH value is 9.0 ~ 13.0 electrochemical deoiling liquid carry out electrochemical deoiling 2 ~ 15 minutes to steel cord, electrochemical deoiling liquid by the concentration of sodium hydroxide be 10 ~ 15g/L, the concentration of sodium silicate be 6 ~ 10g/L, the concentration of sodium carbonate be 15 ~ 30g/L, the proportions that concentration is 1 ~ 5 g/L of OP-10 emulsifying agent forms；G, by through oil removing steel cord through twice tap water clean, twice deionized water clean after, temperature be 25 ~ 40 DEG C, concentration expressed in percentage by volume be 5% ~ 10% sulfuric acid solution in steel cord is carried out pickling 0.5 ~ 5.0 minute, again after the cleaning of twice tap water, twice deionized water clean, complete the pre-treatment of steel cord；
(3) steel cord without the cuprous brass plating of cyanogen: h, step (1) is prepared be warming up to 25 ~ 80 DEG C without cyanogen cuprous brass plating solution, use ruthenium titanium conformal anode, be 0.6 ~ 4.0A/dm in cathode-current density2Under conditions of steel cord is carried out brass plating 2 ~ 30 minutes, then through twice tap water clean, twice deionized water clean after, complete steel cord without the cuprous brass plating of cyanogen.
The steel cord of present embodiment can be with the cuprous chelating agent of selective complexation cuprous ion by with the addition of in without cyanogen cuprous brass plating solution without the cuprous brass plating of cyanogen, when the steel cord through pre-treatment is carried out cyanideless electro-plating pyrite, the brass coating that Coating composition is stable, adhesion is good can be obtained at steel cord surface, not only shorten production process, and reduce production cost.Present embodiment can solve the crucial technical problem that in steel cord actual production, surface cyanideless electro-plating brass coating composition is wayward, binding force of cladding material is poor, is significant for steel cord manufacturing industry.
Detailed description of the invention two: present embodiment antioxidant described in a and b of step (1) unlike detailed description of the invention one is the one in uric acid, vitamin C, sodium hypophosphite, hydroquinone, catechol or resorcinol, and concentration is 0.5 ~ 15.0g/L.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment cuprous chelating agent described in a and b of step (1) unlike detailed description of the invention one or two is a kind of or the most several combination in thiosemicarbazide, tetramethyl thiourea, thiourea or ethylene thiourea, and concentration is 18 ~ 145g/L.Other is identical with detailed description of the invention one or two.
When the cuprous chelating agent of present embodiment is compositions, any combination pressed by various cuprous chelating agent.
Detailed description of the invention four: present embodiment auxiliary complex-former described in a and b of step (1) unlike one of detailed description of the invention one to three is the one in sodium potassium tartrate tetrahydrate, disodiumedetate, trisodium citrate or sodium gluconate, and concentration is 15 ~ 90g/L.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment leveling agent described in d and e of step (1) unlike one of detailed description of the invention one to four is two kinds of combinations by any ratio in ammonium molybdate, gelatin, peptone, stannous sulfate or nickel acetate, and concentration is 0.01 ~ 1.50g/L.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: in present embodiment f of step (2) unlike one of detailed description of the invention one to five be 45 ~ 65 DEG C in temperature, pH value be 9.5 ~ 12.5 electrochemical deoiling liquid in steel cord is carried out electrochemical deoiling 3 ~ 12 minutes, electrochemical deoiling liquid by the concentration of sodium hydroxide be 12 ~ 14g/L, the concentration of sodium silicate be 7 ~ 9g/L, the concentration of sodium carbonate be 16 ~ 25g/L, the proportions that concentration is 2 ~ 4 g/L of OP-10 emulsifying agent forms.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: step (1) is prepared by the h in present embodiment step (3) unlike one of detailed description of the invention one to six to be warming up to temperature without cyanogen cuprous brass plating solution be 30 ~ 70 DEG C, use ruthenium titanium conformal anode, be 0.8 ~ 3.0A/dm in cathode-current density2Under conditions of steel cord is carried out brass plating 2 ~ 30 minutes.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: the Cu consumed in electroplating process without cyanogen cuprous brass plating solution that present embodiment is described unlike one of detailed description of the invention one to seven+And Zn2+Needing periodically to add in plating solution, replenishment method follows the steps below:
(1) take out a part without cyanogen cuprous brass plating solution；(2) according to consuming Cu+And Zn2+Total amount weigh Red copper oxide and zinc oxide, and in case of heating the Red copper oxide weighed and zinc oxide are joined taking-up without in cyanogen cuprous brass plating solution, stirring is until dissolving；(3) by take out add without cyanogen cuprous brass plating solution after refund coating bath.
Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: the passivating method of the brass coating being plated on steel cord described in detailed description of the invention one sequentially includes the following steps:
(1) by the concentration of potassium dichromate be 3 ~ 40g/L, Soluble tartar. na concn be that 5 ~ 20g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, it is added to the water stirring to dissolving, then the pH value using sulphuric acid or potassium hydroxide regulation solution is 4.6 ~ 8.6, obtains chemical passivation liquid；
(2) it is in the chemical passivation liquid prepared of the step (1) of 25 ~ 50 DEG C 2 ~ 15 minutes that the steel cord through brass plating immerses temperature, then cleans through twice tap water, after twice deionized water cleans, completes the passivation of brass coating.
After the present embodiment brass coating to being plated on steel cord uses chemical passivation, complete uniform passivating film can be formed in brass surfaces so that it is corrosion resistance is increased dramatically.
Detailed description of the invention ten: in present embodiment step (1) unlike detailed description of the invention nine by the concentration of potassium dichromate be 5 ~ 35g/L, Soluble tartar. na concn be that 6 ~ 18g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, it is added to the water stirring to dissolving, then the pH value using sulphuric acid or potassium hydroxide regulation solution is 4.8 ~ 8.0, obtains chemical passivation liquid.Other is identical with detailed description of the invention nine.
Detailed description of the invention 11: it is in the chemical passivation liquid prepared of the step (1) of 30 ~ 45 DEG C 3 ~ 12 minutes that the steel cord through brass plating immerses in present embodiment step (2) unlike detailed description of the invention nine or ten temperature, again after the cleaning of twice tap water, twice deionized water clean, complete the passivation of brass coating.Other is identical with detailed description of the invention nine or ten.
By following verification experimental verification beneficial effects of the present invention:
Test one: the steel cord of this test sequentially includes the following steps: without the cuprous brass plating of cyanogen
(1) without the preparation of cyanogen cuprous brass plating solution: a, according to the concentration of Red copper oxide be 20g/L, the concentration of resorcinol be 10.0g/L, the concentration of thiourea be 100g/L, the concentration of ethylene thiourea be 20g/L, the concentration of sodium potassium tartrate tetrahydrate be that 75g/L weighs Red copper oxide, resorcinol, thiourea, ethylene thiourea and sodium potassium tartrate tetrahydrate respectively；B, resorcinol step a weighed, thiourea, ethylene thiourea and sodium potassium tartrate tetrahydrate 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 weighed in step a is joined in solution A, stirring to dissolving, obtained solution B after placing 24 hours；D, be 25g/L according to acetic acid zinc concentration, the concentration of sodium acetate be 45g/L, the concentration of gelatin be 0.10g/L, the concentration of nickel acetate be that 0.25g/L weighs zinc acetate, sodium acetate, gelatin and nickel acetate respectively；E, the zinc acetate weighed in step d, sodium acetate, gelatin and nickel acetate are joined in solution B stirring to dissolving, adjust pH value to 3.5 with acetic acid or ammonia after filtration, join without cyanogen cuprous brass plating solution；
(2) steel cord pre-treatment: f, temperature be 60 DEG C, pH value be 10.5 electrochemical deoiling liquid in steel cord is carried out electrochemical deoiling 5 minutes, electrochemical deoiling liquid by the concentration of sodium hydroxide be 13g/L, the concentration of sodium silicate be 8g/L, the proportions that the concentration that concentration is 20g/L, OP-10 emulsifying agent is 3 g/L of sodium carbonate forms；G, by through oil removing steel cord through twice tap water clean, twice deionized water clean after, temperature be 30 DEG C, concentration expressed in percentage by volume be 8% sulfuric acid solution in steel cord is carried out pickling 1.0 minutes, again after the cleaning of twice tap water, twice deionized water clean, complete the pre-treatment of steel cord；
(3) steel cord without the cuprous brass plating of cyanogen: h, step (1) is prepared be warming up to 50 DEG C without cyanogen cuprous brass plating solution, use ruthenium titanium conformal anode, be 2.0A/dm in cathode-current density2Under conditions of steel cord is carried out brass plating 10 minutes, then through twice tap water clean, twice deionized water clean after, complete steel cord without the cuprous brass plating of cyanogen.
This test obtains the electron scanning micrograph of brass coating at steel cord surface as it is shown in figure 1, from fig. 1, it can be seen that pass through to obtain homogeneous careful brass coating at steel cord surface without the cuprous brass plating of cyanogen.
This test obtains the copper scattergram of brass coating and zinc element scattergram as shown in Figure 2 at steel cord surface, as can be seen from Figure 2, copper and zinc element are evenly distributed in gained brass coating, and copper content is 69.6% in analysis result display coating, zinc element content is 30.4%, has reached the requirement of steel cord surface brass coating.
The Cu consumed in electroplating process without cyanogen cuprous brass plating solution+And Zn2+Needing periodically to add in plating solution, replenishment method follows the steps below:
(1) take out a part without cyanogen cuprous brass plating solution；(2) according to consuming Cu+And Zn2+Total amount weigh Red copper oxide and zinc oxide, and in case of heating the Red copper oxide weighed and zinc oxide are joined taking-up without in cyanogen cuprous brass plating solution, stirring is until dissolving；(3) by take out add without cyanogen cuprous brass plating solution after refund coating bath.
The passivating method of the above-mentioned brass coating being plated on steel cord sequentially includes the following steps:
(1) by the concentration of potassium dichromate be 25g/L, Soluble tartar. na concn be that 16g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, be added to the water stirring to dissolve, then use sulphuric acid or potassium hydroxide regulation solution pH value is 6.0, obtain chemical passivation liquid；
(2) it is in the chemical passivation liquid prepared of the step (1) of 40 DEG C 5 minutes that the steel cord through brass plating immerses temperature, then cleans through twice tap water, after twice deionized water cleans, completes the passivation of brass coating.
Through above-mentioned chemical purification process, obtain passivating film on brass coating surface, according to Electrochemical results, 1/162.6 before the corrosion rate of coating is passivation after passivation.
Test two: this test with test the difference of be steel cord without in the cuprous brass plating of cyanogen without the preparation of cyanogen cuprous brass plating solution: a, according to the concentration of Red copper oxide be 15g/L, the concentration of resorcinol be 10.0g/L, the concentration of thiourea be 80g/L, the concentration of ethylene thiourea be 10g/L, the concentration of sodium potassium tartrate tetrahydrate be that 60g/L weighs Red copper oxide, resorcinol, thiourea, ethylene thiourea and sodium potassium tartrate tetrahydrate respectively；B, resorcinol step a weighed, thiourea, ethylene thiourea and sodium potassium tartrate tetrahydrate 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 weighed in step a is joined in solution A, stirring to dissolving, obtained solution B after placing 24 hours；D, be 20g/L according to acetic acid zinc concentration, the concentration of sodium acetate be 40g/L, the concentration of gelatin be 0.10g/L, the concentration of nickel acetate be that 0.20g/L weighs zinc acetate, sodium acetate, gelatin and nickel acetate respectively；E, the zinc acetate weighed in step d, sodium acetate, gelatin and nickel acetate are joined in solution B stirring to dissolving, adjust pH value to 3.5 with acetic acid or ammonia after filtration, join without cyanogen cuprous brass plating solution.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 with test the difference of be steel cord without in the cuprous brass plating of cyanogen without the preparation of cyanogen cuprous brass plating solution: a, according to the concentration of Red copper oxide be 18g/L, the concentration of hydroquinone be 8.0g/L, the concentration of thiourea be 80g/L, the concentration of thiosemicarbazide be 35g/L, the concentration of sodium gluconate be that 60g/L weighs Red copper oxide, hydroquinone, thiourea, thiosemicarbazide and sodium gluconate respectively；B, hydroquinone step a weighed, thiourea, thiosemicarbazide and sodium gluconate 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 weighed in step a is joined in solution A, stirring to dissolving, obtained solution B after placing 24 hours；D, be 22g/L according to acetic acid zinc concentration, the concentration of sodium acetate be 40g/L, the concentration of peptone be 0.1g/L, the concentration of stannous sulfate be that 0.25g/L weighs zinc acetate, sodium acetate, peptone and stannous sulfate respectively；E, the zinc acetate weighed in step d, sodium acetate, peptone and stannous sulfate are joined in solution B stirring to dissolving, adjust pH value to 4.0 with acetic acid or ammonia after filtration, join without cyanogen cuprous brass plating solution.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: this test is plated in the passivating method of the brass coating on steel cord unlike test one and sequentially includes the following steps:
(1) by the concentration of potassium dichromate be 15g/L, Soluble tartar. na concn be that 10g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, be added to the water stirring to dissolve, then use sulphuric acid or potassium hydroxide regulation solution pH value is 5.6, obtain chemical passivation liquid；
(2) it is in the chemical passivation liquid prepared of the step (1) of 50 DEG C 6 minutes that the steel cord through brass plating immerses temperature, then cleans through twice tap water, after twice deionized water cleans, completes the passivation of brass coating.
Other step is identical with test one with parameter.
Through above-mentioned chemical purification process, obtain passivating film on brass coating surface, according to Electrochemical results, 1/126.8 before the corrosion rate of coating is passivation after passivation.
Claims (10)
1. steel cord is without the method for the cuprous brass plating of cyanogen, it is characterised in that the method sequentially includes the following steps:
(1) without the preparation of cyanogen cuprous brass plating solution: a, according to the concentration of Red copper oxide be 3 ~ 30g/L, the concentration of antioxidant be 0.2 ~ 20.0g/L, the concentration of cuprous chelating agent be 15 ~ 150g/L, the concentration of auxiliary complex-former be that 10 ~ 100g/L weighs Red copper oxide, antioxidant, cuprous chelating agent and auxiliary complex-former respectively；B, antioxidant step a weighed, cuprous chelating 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 weighed in step a is joined in solution A, stirring to dissolving, obtained solution B after placing 24 hours；D, be 5 ~ 40g/L according to acetic acid zinc concentration, the concentration of sodium acetate be 40 ~ 50g/L, the concentration of leveling agent be that 0.005 ~ 2.500g/L weighs zinc acetate, sodium acetate and leveling agent respectively；E, the zinc acetate weighed in step d, sodium acetate and leveling agent are joined in solution B stirring to dissolving, adjust pH value to 3.0 ~ 6.5 with acetic acid or ammonia after filtration, join without cyanogen cuprous brass plating solution；
(2) steel cord pre-treatment: f, to use temperature be 40 ~ 70 DEG C, pH value is 9.0 ~ 13.0 electrochemical deoiling liquid carry out electrochemical deoiling 2 ~ 15 minutes to steel cord, electrochemical deoiling liquid by the concentration of sodium hydroxide be 10 ~ 15g/L, the concentration of sodium silicate be 6 ~ 10g/L, the concentration of sodium carbonate be 15 ~ 30g/L, the proportions that concentration is 1 ~ 5 g/L of OP-10 emulsifying agent forms；G, by through oil removing steel cord through twice tap water clean, twice deionized water clean after, temperature be 25 ~ 40 DEG C, concentration expressed in percentage by volume be 5% ~ 10% sulfuric acid solution in steel cord is carried out pickling 0.5 ~ 5.0 minute, again after the cleaning of twice tap water, twice deionized water clean, complete the pre-treatment of steel cord；
(3) steel cord without the cuprous brass plating of cyanogen: h, step (1) is prepared be warming up to 25 ~ 80 DEG C without cyanogen cuprous brass plating solution, use ruthenium titanium conformal anode, be 0.6 ~ 4.0A/dm in cathode-current density2Under conditions of steel cord is carried out brass plating 2 ~ 30 minutes, then clean through twice tap water, after twice deionized water cleans, complete steel cord without the cuprous brass plating of cyanogen, obtain the brass coating being plated on steel cord.
Steel cord the most according to claim 1 is without the method for the cuprous brass plating of cyanogen, it is characterized in that the antioxidant described in a and b of step (1) is uric acid, vitamin C, sodium hypophosphite, hydroquinone, catechol or resorcinol, concentration is 0.5 ~ 15.0g/L.
Steel cord the most according to claim 1 is without the method for the cuprous brass plating of cyanogen, it is characterized in that the cuprous chelating agent described in a and b of step (1) is a kind of or the most several combination in thiosemicarbazide, tetramethyl thiourea, thiourea or ethylene thiourea, concentration is 18 ~ 145g/L.
Steel cord the most according to claim 1 is without the method for the cuprous brass plating of cyanogen, it is characterized in that the auxiliary complex-former described in a and b of step (1) is the one in sodium potassium tartrate tetrahydrate, disodiumedetate, trisodium citrate or sodium gluconate, concentration is 15 ~ 90g/L.
Steel cord the most according to claim 1 is without the method for the cuprous brass plating of cyanogen, it is characterized in that the leveling agent described in d and e of step (1) is the combination of two kinds in ammonium molybdate, gelatin, peptone, stannous sulfate or nickel acetate, concentration is 0.01 ~ 1.50g/L.
Steel cord the most according to claim 1 is without the method for the cuprous brass plating of cyanogen, it is characterized in that in the f of step (2) be 45 ~ 65 DEG C in temperature, pH value be 9.5 ~ 12.5 electrochemical deoiling liquid in steel cord is carried out electrochemical deoiling 3 ~ 12 minutes, electrochemical deoiling liquid by the concentration of sodium hydroxide be 12 ~ 14g/L, the concentration of sodium silicate be 7 ~ 9g/L, the concentration of sodium carbonate be 16 ~ 25g/L, the proportions that concentration is 2 ~ 4 g/L of OP-10 emulsifying agent forms.
Steel cord the most according to claim 1 is without the method for the cuprous brass plating of cyanogen, it is characterized in that step (1) is prepared by the h in step (3) to be warming up to temperature without cyanogen cuprous brass plating solution be 30 ~ 70 DEG C, use ruthenium titanium conformal anode, be 0.8 ~ 3.0A/dm in cathode-current density2Under conditions of steel cord is carried out brass plating 2 ~ 30 minutes.
8. according to the steel cord described in any one in claim 1 ~ 7 without the method for the cuprous brass plating of cyanogen, it is characterised in that the described Cu consumed in electroplating process without cyanogen cuprous brass plating solution+And Zn2+Needing periodically to add in plating solution, replenishment method follows the steps below:
(1) take out a part without cyanogen cuprous brass plating solution；(2) according to consuming Cu+And Zn2+Total amount weigh Red copper oxide and zinc oxide, and in case of heating the Red copper oxide weighed and zinc oxide are joined taking-up without in cyanogen cuprous brass plating solution, stirring is until dissolving；(3) by take out add without cyanogen cuprous brass plating solution after refund coating bath.
9. the passivating method of the brass coating being plated on steel cord that any one method in claim 1 ~ 8 obtains, it is characterised in that this passivating method is carried out in accordance with the following methods:
(1) by the concentration of potassium dichromate be 3 ~ 40g/L, Soluble tartar. na concn be that 5 ~ 20g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, it is added to the water stirring to dissolving, then the pH value using sulphuric acid or potassium hydroxide regulation solution is 4.6 ~ 8.6, obtains chemical passivation liquid；
(2) it is in the chemical passivation liquid prepared of the step (1) of 25 ~ 50 DEG C 2 ~ 15 minutes that the steel cord through brass plating immerses temperature, then cleans through twice tap water, after twice deionized water cleans, completes the passivation of brass coating.
The passivating method of the brass coating being plated on steel cord the most according to claim 9, it is characterized in that in step (1) by the concentration of potassium dichromate be 5 ~ 35g/L, Soluble tartar. na concn be that 6 ~ 18g/L weighs potassium dichromate and sodium potassium tartrate tetrahydrate, it is added to the water stirring to dissolving, then the pH value using sulphuric acid or potassium hydroxide regulation solution is 4.8 ~ 8.0, obtains chemical passivation liquid；It is in the chemical passivation liquid prepared of the step (1) of 30 ~ 45 DEG C 3 ~ 12 minutes that steel cord through brass plating immerses in step (2) temperature, again after the cleaning of twice tap water, twice deionized water clean, complete the passivation of brass coating.
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| 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 |
| 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 |
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