CN113668027A - Method for manufacturing brass plating layer steel wire, tire bead steel wire, rubber tube steel wire and steel cord - Google Patents
Method for manufacturing brass plating layer steel wire, tire bead steel wire, rubber tube steel wire and steel cord Download PDFInfo
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- CN113668027A CN113668027A CN202110866234.4A CN202110866234A CN113668027A CN 113668027 A CN113668027 A CN 113668027A CN 202110866234 A CN202110866234 A CN 202110866234A CN 113668027 A CN113668027 A CN 113668027A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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Abstract
The invention discloses a method for manufacturing brass plating steel wires, bead steel wires, rubber tube steel wires and steel cords, which relates to the technical field of steel wire production and manufacture and comprises the following production steps: (1) obtaining a steel wire matrix with a clean surface; (2) applying current to ensure that copper and zinc in the plating solution are codeposited on the surface of the steel wire matrix to form brass alloy; (3) washing the surface of the brass plated steel wire with water; (4) performing surface oxidation resistance treatment on the plated steel wire after washing, and then taking up the steel wire; (6) the bead wire can be directly obtained from (5), and the rubber tube and the steel cord are respectively obtained from (5) through wet drawing and drawing/twisting. Compared with existing cyaniding electroplating and thermal diffusion electroplating, the production method disclosed by the invention is non-toxic and environment-friendly, the process is simple, the component content of the steel wire coating is uniform, gradient distribution is avoided, the stability of the extraction force of vulcanized steel wires and rubber is facilitated, the excellent binding force is realized, the loss of the coating formed by drawing and twisting is favorably controlled, and the production cost and the production efficiency are further facilitated.
Description
Technical Field
The invention belongs to the technical field of brass steel wire manufacturing, and particularly relates to a method for manufacturing a brass plating steel wire, a tire bead steel wire, a rubber tube steel wire and a steel cord.
Background
The brass alloy is widely applied to products such as steel cords, rubber tube steel wires, tire bead steel wires and related decorations due to the excellent adhesive property with rubber and the gorgeous appearance. The early generation electroplating alloy is mainly a cyanide electroplating process, a cyanide electroplated brass plating layer is compact and has excellent plating layer binding force, but with the development of the world and the enhancement of environmental awareness of people, cyanide electroplating is gradually eliminated due to the severe toxicity and chromate passivation after plating, which are not beneficial to personal safety and violate related environmental regulations.
The research on the cyanide-free electroplating process is not interrupted, such as a tartrate system, a pyrophosphate system, an HEDP system and the like, but at present, brass alloy is electroplated by a thermal diffusion method mainly adopted for large-scale production of brass electroplated steel wires at home and abroad, the specific process is to plate copper and then plate zinc, obtain brass plated steel wires by medium-frequency thermal diffusion, phosphorization and soap dipping, the electroplating process is long, the medium-frequency energy consumption is high, phosphorus-containing wastewater is generated, and pyrophosphate copper plating has the problem that the steel wire substrate and the plating solution are displaced, so that the plating binding force is easy to cause poor, the plating loss of steel wire drawing and twisting is increased, and the production cost and the production efficiency are unfavorable.
Therefore, there is a need for a method of manufacturing brass-plated steel wire that avoids the highly toxic and passivation treatment and the thermal diffusion plating process of conventional cyanide plating.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for manufacturing a brass plated steel wire, a tire bead steel wire, a rubber tube steel wire and a steel cord, which has simple process and environmental protection.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a method of making a brass coated steel wire, comprising the steps of:
obtaining a steel wire matrix with a clean surface;
co-depositing copper and zinc in the plating solution on the surface of the steel wire substrate by an electroplating method to form a brass steel wire;
washing the surface of the brass steel wire with water to obtain a plated steel wire after washing with water;
and (4) carrying out surface antioxidant treatment on the washed plated steel wire and then taking up the steel wire to obtain the brass plated steel wire.
Further, the method for co-depositing copper and zinc in the plating solution on the surface of the steel wire substrate to form brass by the electroplating method comprises the following steps:
installing the steel wire substrate on a cathode of an electroplating device, and injecting plating solution into the aqueduct;
a brass cylinder with the length and the width of about 1cm is adopted at the anode, and the distance between the brass cylinder and the cathode is 1-2 cm; the current density of electroplating is 10-30A/dm 2;
controlling the temperature of the plating solution to be 45-50 ℃, and electroplating by adopting a steady flow and barrel plating mode.
Further, the plating solution is a polyphosphate plating solution, and comprises a potassium ammonium salt complexing agent, copper salt and zinc salt thereof; the preparation process of the plating solution comprises the following steps: preheating pure water to 50-60 ℃, adding a complexing agent into the pure water, stirring, adding a zinc salt into the pure water, stirring after the complexing agent is dissolved, adding a copper salt into the pure water after the zinc salt is dissolved, stirring until the zinc salt is dissolved, and completing the preparation of a plating solution; the contents of the complexing agent, the copper ions and the zinc ions in the plating solution are 240 +/-10 g/L, 16 +/-1 g/L and 5 +/-1 g/L respectively; the pH value of the plating solution is 10.7-11.3.
Further, the method for washing the surface of the brass plated steel wire comprises the following steps: the brass steel wire is firstly washed with water at normal temperature and then washed with water at high temperature.
Furthermore, normal temperature washing is carried out with parallel multisection washing mode, and the washing is by back festival to front festival overflow, and first festival washing is by overflow pipe to coating bath, and the cleaning time is in 2~4s, and parallel washing festival number control is in 4~8 festival.
Further, the washing time of the high-temperature washing is 3-5 s, and the washing temperature is 65-90 ℃.
Further, the method for carrying out surface oxidation resistance treatment on the washed steel wire with the plated layer comprises the following steps:
and (3) treating the steel wire with the water-washed plated layer at 85 ℃ for 4 seconds by adopting an aqueous solution of alkyl polyoxyethylene ether potassium phosphate, polyoxyethylene alkylamine and sodium hypophosphite before naturally drying.
In a second aspect, the present invention provides a method of making a brass-plated bead wire, including the method of making a brass-plated wire of the first aspect.
In a third aspect, the present invention provides a method for manufacturing a brass-plated steel wire for a hose, including the method for manufacturing a brass-plated steel wire according to the first aspect, further including the steps of:
and carrying out wet drawing on the brass plated steel wire after the wire is taken up to obtain the rubber tube steel wire.
In a fourth aspect, the present invention provides a method for manufacturing a brass-plated steel cord, comprising the method for manufacturing a brass-plated steel wire of the first aspect, further comprising the steps of:
and carrying out wet drawing on the brass plated steel wire after the wire is taken up to obtain a monofilament, and twisting the monofilament to obtain the steel cord.
Compared with the prior art, the invention has the following beneficial effects:
1. the plating solution provided by the invention is simple and clean, and the plating solution and the using method thereof overcome the defects of a cyaniding method, such as high toxicity, high danger, complex cyanide-containing sewage treatment, high environmental protection cost and the like; the defects of complex process, high maintenance and management difficulty, high energy consumption and the like of the thermal diffusion method are overcome.
2. The invention can obtain more uniform, continuous and compact brass plating, has clean and easy process, is simple and environment-friendly and has great application prospect.
3. The electroplating coating has uniform components, no copper-zinc gradient, is favorable for stabilizing the drawing force of vulcanized steel wires and rubber, has tight combination of the coating and enhanced compactness of the coating, reduces the loss of the subsequent drawing and twisting coating, and is favorable for saving the production cost and improving the production efficiency.
Drawings
FIG. 1 is a process flow chart of the method for manufacturing a brass plated steel wire and the bead wire, hose wire and steel cord thereof;
FIG. 2 is a bar graph showing the uniformity of the coating content of the brass-plated steel wire of the example;
FIG. 3 is a comparison of the plated self-winding of brass-plated steel wires and thermal diffusion plated steel wires in examples.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The first embodiment is as follows:
the invention provides a method for manufacturing a brass plated steel wire, which comprises the following steps:
obtaining a steel wire matrix with a clean surface;
co-depositing copper and zinc in the plating solution on the surface of the steel wire substrate by an electroplating method to form brass;
washing the surface of the brass steel wire with water to obtain a plated steel wire after washing with water;
and (4) carrying out surface antioxidant treatment on the washed plated steel wire and then taking up the steel wire to obtain the brass plated steel wire.
The plating solution is a polyphosphate plating solution, and comprises a potassium-ammonia salt complexing agent, copper salt and zinc salt thereof.
The plating solution is used for preparing a uniform, continuous and compact brass plating layer with strong bonding force with a matrix, and the plating layer quality such as copper-zinc ratio, thickness and the like of the plating layer meets the technical requirements of GB/T24245-2009 steel cord for rubber tracks and related national standards.
The preparation process of the plating solution comprises the following steps: firstly, a certain amount of pure water is taken, preheated to 50-60 ℃, then a quantitative potassium ammonium polyphosphate complexing agent is added into the pure water and stirred, a quantitative zinc polyphosphate salt is added and stirred after the pure water is dissolved, a quantitative copper polyphosphate salt can be added after the zinc salt is dissolved, the mixture is stirred until the zinc salt is dissolved, and the plating solution is prepared for standby. The pH of the plating solution is not required to be adjusted by adding other medicines, and the concentration of the plating solution is monitored every day, and the complexing agent is quantitatively supplemented.
Electroplating parameters in the plating process: a. the contents of complexing agent, copper ions and zinc ions in the polyphosphate electroplating solution are in the ranges of 240 +/-10 g/L, 16 +/-1 g/L and 5 +/-1 g/L; b. the temperature of the plating solution is 45-50 ℃; c. the pH value of the plating solution is 10.7-11.3; d. the anode is a brass cylinder with the length and the width of about 1cm and is spaced from the cathode by 1-2 cm; e. the current density is 10-30A/dm2(ii) a f. The electroplating adopts a steady flow and barrel plating mode, namely a copper zinc layer with required proportion is deposited on the surface of the steel wire simultaneously.
The matters to be taken into consideration during electroplating: the steel wire is used as a cathode, the surface of the steel wire is required to be clean, and the steel wire is not in contact with the anode; the plating solution is circulated ceaselessly to prevent the local temperature from being overhigh; the steel wires in the wiring are not crossed and parallel; the components of the plating solution are required to be detected every day, and the complexing agent is required to be supplemented in time.
The plating solution provided by the invention is simple and clean, and overcomes the defects of high toxicity, high danger, complex cyanide-containing sewage treatment, high environmental protection cost and the like of the cyanide plating solution; the using method overcomes the defects of complex process, high maintenance and management difficulty, high energy consumption and the like of a thermal diffusion method. The embodiment can obtain more uniform, continuous and compact brass plating, and the process is clean and easy to implement, thereby having great application prospect.
Specifically, the method for washing the surface of the brass plated steel wire comprises the following steps: the brass steel wire is firstly washed with water at normal temperature and then washed with water at high temperature. Normal temperature water washing is carried out in a parallel multi-section water washing mode, water washing overflows from a rear section to a front section, first section water washing is carried out from an overflow pipeline to a plating tank, the washing time is 2-4 s, and the number of parallel water washing sections is controlled to be 4-8 sections. The washing time of the high-temperature washing is 3-5 s, and the washing temperature is 65-90 ℃.
Specifically, the method for performing surface oxidation resistance treatment on the plated steel wire after washing comprises the following steps: and (3) before the steel wire coated with the coating is naturally dried after being washed by water, treating the steel wire at 85 ℃ for 4 seconds by using a water-based coating solution containing 5 parts of alkyl polyoxyethylene ether potassium phosphate, 2 parts of polyoxyethylene alkylamine and 2 parts of sodium hypophosphite, and taking up the steel wire.
The specific production process and coating parameters of the brass coated steel wire are shown in table 1, wherein the steel wires of 0.82mm, 0.95mm and 1.25mm are heat-treated steel wires after being subjected to electrolytic alkali cleaning, electrolytic acid cleaning and chemical acid cleaning for rust removal, and the steel wires of 1.50mm and above the specification in the embodiment are continuously drawn steel wires after being subjected to mechanical grinding or chemical acid cleaning for rust removal.
The production process of the present invention will now be described in detail by taking number A as an example, which is as follows: the concentration of a plating solution complexing agent, copper ions and zinc ions of the heat-treated wire with the diameter of 0.95mm after rust removal is 230g/L, 15g/L and 4g/L respectively, the pH value is 10.7, the temperature is 45 ℃, and the current density is 10A/dm2Applying current under the condition, electroplating the steel wire in a barrel plating mode for 0.12min, washing the steel wire out of the plating tank with 4 sections of normal-temperature water, then washing with high-temperature water flow at the washing temperature of 65 ℃ for 5s, treating the steel wire in a surface anti-oxidation treatment tank at the temperature of 85 ℃ for 4s, and naturally air-drying and taking up the steel wire to obtain the required brass plated steel wire. The parameter changes of the steel wires with other numbers are shown in the table 1, and the specific production modes are all carried out as the above example.
TABLE 1 detailed production process and coating parameters of brass-coated steel wire of the present invention
Example two:
this example provides a method for producing a brass-plated bead wire, which obtained 0.95mm, 1.55mm and 2.20mm brass-plated bead wires from the steel wires of nos. a to C, respectively.
For bead wire products, the market is mainly based on bronze, brass and pure zinc plating, but the brass plating is optimally bonded to the rubber (CN 104694982A). The conventional bead plating layer is mostly bronze, and is used for common radial tires, and the brass bead is mostly used for special performance tires such as aviation tires, load tires, engineering tires and the like. Table 2 shows the comparative data of the parameters of the plating layer and the vulcanization extraction force between the brass plated bead wire of the present invention and the bead wires of bronze and pure zinc layers of the same specification, the vulcanization sizing material and the vulcanization conditions are consistent, the absolute difference of the thickness of the steel wire plating layer is within 0.03um, and it can be seen that the plated bead wire of the present invention is used for bead wire products, and has excellent binding force with rubber. The prior art for plating brass on the surface of the tire bead steel wire mainly comprises cyanidation and thermal diffusion electroplating, wherein the toxicity and the wastewater treatment complexity of the cyanidation electroplating are gradually replaced, the thermal diffusion electroplating process is long, and the problem that the steel wire matrix and the plating solution are replaced exists.
TABLE 2 vulcanization drawing-out force and coating parameters of bead wires with different coatings
Example three:
in this example, 0.152mm, 0.295mm, 0.35mm, 0.50/0.56mm and 0.65/0.70mm rubber tube steel wires were obtained by wet drawing on brass-plated steel wires numbered D to H.
Example four:
in this example, brass plated steel wires of nos. I to L were subjected to drawing and twisting to obtain 3922, 0230/0330, 2730, and 16320 steel cords, respectively.
The steel wire with the coating is used for rubber tube steel wires and steel cord products, the brass coating of the steel wire has no copper-zinc gradient, the content of each component is uniform from the inner layer to the outer layer, the stability of the drawing force of the steel wire and rubber is favorably maintained, the binding force of the coating is excellent, and the loss of the coating formed by drawing and twisting is favorably controlled.
In order to verify the above discussion, the steel wire of the embodiment with the conventional coating thickness is subjected to the detection of the content of the full coating, the detection of 1 gCu% on the surface and the self-winding test, specifically, the steel wire coatings with numbers D to F and I to L are subjected to the detection of Cu% and 1 gCu% on the surface, the detection results are shown in FIG. 2, the absolute difference values of the detection results of the two are 0.06-0.14%, and the uniformity of the internal and external contents of the components of the coating is illustrated. Table 3 shows the coating parameters of the thermal diffusion brass steel wires of each specification. Table 4 shows comparative data of drawing force of finished steel wires with numbers D-F and I-L, steel wires with the same specification of thermal diffusion and rubber vulcanization, the executed sizing materials are consistent with the steel wires with the same specification of vulcanization conditions, the difference of percentage copper of the coating of the comparative steel wires is within +/-0.15%, and the difference of thickness of the coating is within 0.2um, and the data in Table 4 show that the coated steel wires are more beneficial to maintaining the stability of the drawing force.
FIG. 3 shows the different current densities (10, 20, 30A/dm)2) The self-winding contrast diagram of the steel wire of the invention and the thermal diffusion electroplated steel wire with the same specification shows that the current density of the steel wire of the invention increases progressively in the direction of an arrow, and the current density of the thermal diffusion steel wire is 13A/dm2And the difference of the thickness of the plating layer of the comparative steel wire is within 0.2um, and the difference of the percentage copper of the plating layer is within +/-0.15 percent. FIG. 3 illustrates that the surface of the steel wire with the coating of the invention has bright and uniform color, smooth feeling, no dew point phenomenon in the self-winding test, slightly dull and rough surface of the steel wire with thermal diffusion, and slight surface pit phenomenon of the steel wire after self-winding, which indicates that the coating binding force of the steel wire with the coating of the invention is superior to that of the steel wire with thermal diffusion.
Table 5 shows the comparative data of the drawing and twisting losses of the steel wire of this embodiment and the plating layer of the thermal diffusion steel wire of the same specification, the difference of the plating thickness of the comparative steel wire is within 0.2um, the difference of the percentage copper of the plating layer is within ± 0.15%, and the drawing and twisting processes are the same. It can be seen from table 5 that the drawing and twisting loss of the plated steel wire of the present invention is lower than that of the thermal diffusion steel wire, i.e., the plated steel wire of the present invention is advantageous for controlling the drawing and twisting loss of the plating layer, thereby contributing to the saving of the production cost and the improvement of the production efficiency.
TABLE 3 coating parameters of heat-diffusion brass comparative wires
TABLE 4 comparison of the pullout force of the finished steel wire and the thermal diffusion steel wire of the same specification in each example
TABLE 5 comparative data on the coating loss of brass steel wires according to the invention and thermal diffusion steel wires
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, parameter, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, parameters, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A method of making a brass coated steel wire, comprising the steps of:
obtaining a steel wire matrix with a clean surface;
co-depositing copper and zinc in the plating solution on the surface of the steel wire substrate by an electroplating method to form a brass steel wire;
washing the surface of the brass steel wire with water to obtain a plated steel wire after washing with water;
and (4) carrying out surface antioxidant treatment on the washed plated steel wire and then taking up the steel wire to obtain the brass plated steel wire.
2. The method of manufacturing a brass-plated steel wire in accordance with claim 1, wherein the method of forming brass by co-depositing copper and zinc in a plating solution on the surface of the steel wire substrate by an electroplating method comprises:
installing the steel wire matrix on a cathode of an electroplating device, and injecting a plating solution into a plating tank;
a brass cylinder with the length and the width of about 1cm is adopted at the anode, and the distance between the brass cylinder and the cathode is 1-2 cm; the current density of electroplating is 10-30A/dm2；
Controlling the temperature of the plating solution to be 45-50 ℃, and electroplating by adopting a steady flow and barrel plating mode.
3. The method of claim 2, wherein the plating solution is a polyphosphate plating solution comprising a potassium ammonium salt complexing agent, a copper salt and a zinc salt thereof;
the preparation process of the plating solution comprises the following steps: preheating pure water to 50-60 ℃, adding a complexing agent into the pure water, stirring, adding a zinc salt into the pure water, stirring after the complexing agent is dissolved, adding a copper salt into the pure water after the zinc salt is dissolved, stirring until the zinc salt is dissolved, and completing the preparation of a plating solution;
the contents of the complexing agent, the copper ions and the zinc ions in the plating solution are 240 +/-10 g/L, 16 +/-1 g/L and 5 +/-1 g/L respectively; the pH value of the plating solution is 10.7-11.3.
4. The method of manufacturing a brass-plated steel wire as set forth in claim 1, wherein the step of washing the surface of the brass-plated steel wire with water comprises: the brass steel wire is firstly washed with water at normal temperature and then washed with water at high temperature.
5. The method according to claim 4, wherein the normal temperature washing is performed in multiple stages in parallel, the washing overflows from the rear stage to the front stage, the first stage is performed in the overflow pipe to the plating tank, the washing time is 2-4 s, and the number of stages of parallel washing is controlled to 4-8 stages.
6. The method for manufacturing a brass-plated steel wire in accordance with claim 4, wherein the high-temperature washing is carried out for 3 to 5 seconds at a temperature of 65 to 90 ℃.
7. The method of manufacturing a brass-plated steel wire as recited in claim 1, wherein the step of subjecting the washed plated steel wire to a surface oxidation resistance treatment comprises:
and (3) treating the steel wire with the water-washed plated layer at 85 ℃ for 4 seconds by adopting an aqueous solution of alkyl polyoxyethylene ether potassium phosphate, polyoxyethylene alkylamine and sodium hypophosphite before naturally drying.
8. A method of making a brass-plated bead wire, comprising the method of making a brass-plated wire of any one of claims 1 to 7.
9. A method of making a brass-plated steel wire for a hose, comprising the method of making a brass-plated steel wire of any one of claims 1 to 7, further comprising the steps of:
and carrying out wet drawing on the brass plated steel wire after the wire is taken up to obtain the rubber tube steel wire.
10. A method of making a brass-plated steel cord comprising the method of making a brass-plated steel wire of any one of claims 1 to 7, further comprising the steps of:
and carrying out wet drawing on the brass plated steel wire after the wire is taken up to obtain a monofilament, and twisting the monofilament to obtain the steel cord.
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| 代海宁主编: "《电化学基本原理及应用》", vol. 2014, 冶金工业出版社, pages: 22 - 23 * |
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