WO2020034241A1 - Tire bead wire having multiple platings and plating method for platings thereof - Google Patents

Tire bead wire having multiple platings and plating method for platings thereof Download PDF

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Publication number
WO2020034241A1
WO2020034241A1 PCT/CN2018/101709 CN2018101709W WO2020034241A1 WO 2020034241 A1 WO2020034241 A1 WO 2020034241A1 CN 2018101709 W CN2018101709 W CN 2018101709W WO 2020034241 A1 WO2020034241 A1 WO 2020034241A1
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Prior art keywords
copper
plating
bead wire
plating solution
coating
Prior art date
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PCT/CN2018/101709
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French (fr)
Chinese (zh)
Inventor
李文军
Original Assignee
山东大业股份有限公司
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Publication of WO2020034241A1 publication Critical patent/WO2020034241A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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

Definitions

  • the invention relates to the field of bead wire production, in particular to a bead wire with multiple plating layers and a method for plating the same.
  • the bead wire must withstand extremely complex alternating and impact loads during the use of the tire, this requires that the bead wire must have good adhesion to the rubber. On the contrary, the tire tends to cause loose travellers during use, The wire puncture can even cause accidents such as bead blasting that endanger personal and property safety.
  • the adhesion between smooth steel wire and rubber is extremely poor, it is necessary to cover the surface of the steel wire with a uniform coating.
  • the bonding force between the copper-plated bead wire and rubber is mainly reflected in two kinds of forces, including chemical bonding formed by the chemical reaction between the copper sulfide layer produced after vulcanization and rubber, and vulcanization formed by the highly polar rubber surface and the surface of the steel wire.
  • the physical bonding between the cuprous films, these two forms of bonding forces work together to make a good bond between the steel wire and the rubber.
  • the surface coating of the bead wire can be selected from single metals or binary alloys such as pure copper, tin bronze, brass, and pure zinc.
  • the adhesion between steel wire and rubber is not only determined by the steel wire, but also closely related to the rubber formula.
  • the main factors affecting the adhesion performance are the bead wire coating composition, coating thickness, and surface condition. Due to the different rubber types of different tires, different plating layers need to be selected according to the rubber type and needs of the user to adapt to the corresponding rubber characteristics during production. This requires the construction of multiple different copper plating production lines, or a production line equipped with multiple copper plating devices. This will cause difficulties in setting up the factory production line and normal process arrangements, and increase production costs.
  • the present invention provides a bead wire with multi-layer coating suitable for a variety of rubbers and a plating method thereof to solve the problem that a single copper or alloy coating cannot match a variety of tire rubbers at present.
  • the invention provides a bead wire with multiple plating layers, wherein the multiple plating layer on the surface of the bead wire is composed of three layers, wherein the three layers are a copper-tin alloy coating and a copper-nickel alloy coating from the inside to the outside, respectively. And copper-zinc alloy coating.
  • the bead wire with multiple plating layers wherein the copper-tin alloy coating is 0.03-0.09 ⁇ m, the thickness of the copper-nickel alloy coating is 0.02-0.08 ⁇ m, the thickness of the copper-zinc alloy coating is 0.02-0.08 ⁇ m, and the three-layer coating The total thickness is 0.1-0.15 ⁇ m.
  • the bead wire with multiple plating layers wherein the copper content of the copper-tin alloy coating layer is 0.5% -12%, the nickel content of the copper-nickel alloy coating layer is 50% -70%, and the copper content of the copper-zinc alloy coating layer is zinc. The content is 30% -40%.
  • the plating method for a bead wire with multiple plating layers as described above includes the following steps:
  • the bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.03-0.09 ⁇ m; and then washed with water;
  • step S3 The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution, and the surface of the bead wire is plated with a copper-nickel alloy layer having a thickness of 0.02-0.08 ⁇ m; and then washed with water;
  • step S4 The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution, and the surface of the bead wire is plated with a copper-zinc alloy coating having a thickness of 0.02-0.08 ⁇ m; and then washed and dried. A bead wire having three multi-layer coatings on its surface was obtained.
  • the copper-tin alloy plating solution includes the following components:
  • the copper-nickel alloy plating solution includes the following components in mass concentration:
  • Potassium pyrophosphate 110-130g / L;
  • the pH of the plating solution is 8.5-9.5.
  • the copper-zinc alloy plating solution includes the following components in mass concentration:
  • Potassium pyrophosphate 110-130g / L;
  • the pH value of the plating solution is 10-11.
  • the copper plating temperature in step S2 is 30-40 ° C
  • the copper plating temperature in step S3 is 45-55 ° C
  • the copper plating temperature in step S4 is 45-55 ° C.
  • the travel speed of the bead wire in the three plating solutions is 350-400 m / min.
  • the multi-layer plating provided by the present invention is specially used for copper plating on the surface of the bead wire.
  • the bead wire with multi-layer plating can be applied to various types of rubber such as high sulfur rubber and low sulfur rubber, which has a wide range of applications and greatly simplifies. Set up factory production lines and reduce production costs;
  • the multi-layer coating consisting of copper-tin alloy coating, copper-nickel alloy coating and copper-zinc alloy coating provided inside and outside improves the binding force of the bead wire and rubber by more than 6%.
  • the plating method provided by the present invention significantly improves the plating speed of the bead wire surface coating, and the traveling speed during the bead wire plating process is increased to 350-400m / min, which is 1.5 times that of the traditional single plating. -2 times, thereby greatly improving the production efficiency of the bead wire with multi-layer plating and reducing the production cost.
  • the invention provides a bead wire with multiple plating layers, wherein the multiple plating layer on the surface of the bead wire is composed of three layers, wherein the three layers are a copper-tin alloy coating and a copper-nickel alloy coating from the inside to the outside, respectively. And copper-zinc alloy coating.
  • the copper-tin alloy plating layer in the innermost layer serves as a base
  • the copper-nickel alloy plating layer in the middle layer serves as a transition layer to prevent corrosion.
  • the copper-zinc alloy plating layer in the outermost layer mainly plays a role of bonding with rubber.
  • the combination of copper-tin alloy coating and copper-nickel alloy coating and copper-zinc alloy coating further improves the adhesion between the multi-layer coating and rubber, and also improves the anti-corrosion and rust-proof performance of the bead wire.
  • the copper-tin alloy coating is 0.03-0.09 ⁇ m
  • the thickness of the copper-nickel alloy coating is 0.02-0.08 ⁇ m
  • the thickness of the copper-zinc alloy coating is 0.02-0.08 ⁇ m
  • the total thickness of the three-layer coating is 0.1-0.15 ⁇ m
  • the total thickness of the three plating layers is 0.1-0.15 ⁇ m.
  • the thickness of the multi-plated coating provided above is optimal, which not only greatly improves the adhesion between the multi-plated coating and various rubbers, but also maintains the normal mechanical properties of the bead wire, and is less prone to rusting.
  • the excessive thickness of the above-mentioned multi-layer plating will cause the cohesion of the plating interface to be destroyed, resulting in a decrease in the adhesion between the plating layers and a decrease in the adhesion between the multi-layer plating and the rubber.
  • the rust ability is reduced, and the comprehensive performance of the coating is reduced.
  • the tin content of the copper-tin alloy coating is 0.5% -12%
  • the nickel content of the copper-nickel alloy coating is in the range of 50% -70%
  • the copper content of the copper-zinc alloy coating is 30% -40%.
  • the setting in accordance with the thickness and position distribution of the multi-layer coating makes the comprehensive performance of the multi-layer alloy coating good, and it has a large adhesive force with various rubbers (high sulfur rubber, low sulfur rubber, etc.), and has a wide application range.
  • the plating method for the above-mentioned multi-plated bead wire includes the following specific steps:
  • a copper-tin alloy plating solution, a copper-nickel alloy plating solution, and a copper-zinc alloy plating solution are respectively configured according to the following formula; wherein the copper-tin alloy plating solution includes the following concentrations of components:
  • the copper-nickel alloy plating solution includes the following components in mass concentration:
  • Potassium pyrophosphate 110-130g / L;
  • the pH of the plating solution is 8.5-9.5.
  • the copper-zinc alloy plating solution includes the following components in mass concentration:
  • Potassium pyrophosphate 110-130g / L;
  • the pH value of the plating solution is 10-11.
  • the three types of plating solutions described above are arranged using water as a solvent.
  • the three methods of configuring the above plating solutions are: adding purified water to the corresponding plating baths, and then adding a fixed amount of each component, mixing them uniformly, adjusting the pH value, and heating the plating solutions to the corresponding copper plating temperatures. .
  • the three types of coatings mentioned above have few types of raw materials, are easy to collect, simple to configure, do not require complicated experimental equipment, and are easy to operate.
  • the three types of plating solutions prepared by the above formulas have fast formation of coatings and stable multi-layer coatings on the surface of steel wires. , Strong binding ability with rubber, wide range of use.
  • the bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the bead wire surface is plated with a copper-tin alloy coating having a thickness of 0.03-0.09 ⁇ m, and the copper plating temperature is 30-40 ° C; then washed with water.
  • step S3 The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the bead wire surface is plated with copper-nickel having a thickness of 0.02-0.08 ⁇ m. Alloy plating; then washed with water.
  • step S4 The bead wire treated in step S3 is electroplated through a plating bath containing a copper-zinc alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the surface of the bead wire is coated with copper-zinc with a thickness of 0.02-0.08 ⁇ m. Alloy plating; and then washed and dried to obtain a bead wire with three multi-layer plating on its surface.
  • the travel speed of the bead wire in the three plating solutions is 350-400m / min. Compared with the traditional plating speed of 200-300m / min, the travel speed of bead wire plating is increased by 1.5-2 times. Because each plating solution forms a plating layer on the surface of the bead wire at a high speed, the travel speed of the bead wire can not only meet the requirements of electroless plating, but also greatly improve the work efficiency and reduce the production cost of electroless plating.
  • This embodiment provides a plating method for a bead wire with multiple plating layers. The specific steps are as follows:
  • the copper-tin alloy plating solution includes the following components: CuSO 4 ⁇ 5H 2 O: 16g / L;
  • the copper-nickel alloy plating solution includes the following components in mass concentration: CuSO 4 ⁇ 5H 2 O: 7g / L;
  • NiSO 4 ⁇ 6H 2 O 15 g / L; potassium pyrophosphate: 110-130 g / L; wherein the pH of the plating solution is 8.5-9.5.
  • the copper-zinc alloy plating solution includes the following components in mass concentration: CuSO 4 ⁇ 5H 2 O: 10g / L; ZnSO 4 ⁇ 7H 2 O: 11g / L; potassium pyrophosphate: 110-130g / L; wherein, The pH of the plating solution is 10-11.
  • the bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.09 ⁇ m, and the copper plating temperature is 30-40 ° C; Then wash with water.
  • step S3 The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the surface of the bead wire is plated with a copper-nickel alloy layer with a thickness of 0.02 ⁇ m. ; Then wash with water.
  • step S4 The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the bead wire surface is coated with a copper-zinc alloy coating with a thickness of 0.02 ⁇ m. ; Then washing and drying treatment to obtain a bead wire with three multi-layer plating on its surface.
  • the travel speed of the bead wire in the three plating solutions is 350 m / min.
  • the prepared bead wire with multiple plating layers has three layers, the bottom layer is a copper-tin alloy coating, the middle is a copper-nickel alloy coating, and the surface layer is a copper-zinc alloy coating.
  • the copper-tin alloy coating is 0.09 ⁇ m
  • the thickness of the copper-nickel alloy coating is 0.02 ⁇ m
  • the thickness of the copper-zinc alloy coating is 0.02 ⁇ m.
  • the steel wire used in this embodiment is national standard 72 steel, and the wire diameter is 0.96 mm.
  • a conventional steel wire of the same type coated with a single copper alloy coating of the same thickness was used as a control group, and the bead wire with a multi-layer coating in this embodiment was used as an experimental group.
  • the adhesion of the two sets of bead wires to vulcanized rubber was tested. .
  • the specific test method is: put the refined homogeneous rubber compound into a vulcanization mold, and place the experimental group and a control group in the middle of the rubber compound respectively, vulcanize with a flat plate vulcanizer, and cool the rubber compound through Instron pull force The maximum force obtained by the machine when the bead wire of the three experimental groups was pulled out of the rubber compound was the adhesion force.
  • test results were as follows: the adhesion between the control group and rubber was 1020N, the adhesion between the experimental group and rubber was 1095N, and the adhesion of the experimental group increased by 7.3%.
  • This embodiment provides a plating method for a bead wire with multiple plating layers. The specific steps are as follows:
  • the copper-tin alloy plating solution includes the following components: CuSO 4 ⁇ 5H 2 O: 10 g / L;
  • the copper-nickel alloy plating solution includes the following components in mass concentration: CuSO 4 ⁇ 5H 2 O: 13 g / L;
  • NiSO 4 ⁇ 6H 2 O 25 g / L; potassium pyrophosphate: 110-130 g / L; wherein the pH of the plating solution is 8.5-9.5.
  • the copper-zinc alloy plating solution includes the following components in mass concentration: CuSO 4 ⁇ 5H 2 O: 10g / L; ZnSO 4 ⁇ 7H 2 O: 11g / L; potassium pyrophosphate: 110-130g / L; The pH of the plating solution is 10-11.
  • the bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the bead wire surface is plated with a copper-tin alloy coating having a thickness of 0.03 ⁇ m, and the copper plating temperature is 30-40 ° C; Then wash with water.
  • step S3 The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the surface of the bead wire is plated with a copper-nickel alloy layer with a thickness of 0.08 ⁇ m. ; Then wash with water.
  • step S4 The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the bead wire surface is coated with a copper-zinc alloy coating with a thickness of 0.02 ⁇ m. ; Then washing and drying treatment to obtain a bead wire with three multi-layer plating on its surface.
  • the travel speed of the bead wire in the three plating solutions is 400 m / min.
  • the prepared bead wire with multiple plating layers has three layers, the bottom layer is a copper-tin alloy coating, the middle is a copper-nickel alloy coating, and the surface layer is a copper-zinc alloy coating.
  • the thickness of the copper-tin alloy coating is 0.03 ⁇ m
  • the thickness of the copper-nickel alloy coating is 0.08 ⁇ m
  • the thickness of the copper-zinc alloy coating is 0.02 ⁇ m.
  • the experimental group and the control group of this embodiment both use GB 80 steel wire with a wire diameter of 1.2 mm.
  • the method for testing the adhesion force in this embodiment is the same as the method in embodiment 1.
  • test results were as follows: the adhesion between the control group and rubber was 1015N, the adhesion between the experimental group and rubber was 1090N, and the adhesion of the experimental group increased by 7.8%.
  • This embodiment provides a plating method for a bead wire with multiple plating layers. The specific steps are as follows:
  • the copper-tin alloy plating solution includes the following components: CuSO 4 ⁇ 5H 2 O: 13g / L;
  • the copper-nickel alloy plating solution includes the following components in mass concentration: CuSO 4 ⁇ 5H 2 O: 10 g / L;
  • NiSO 4 ⁇ 6H 2 O 20 g / L; potassium pyrophosphate: 110-130 g / L; wherein the pH of the plating solution is 8.5-9.5.
  • the copper-zinc alloy plating solution includes the following components in mass concentration: CuSO 4 ⁇ 5H 2 O: 15g / L; ZnSO4 ⁇ 7H 2 O: 16g / L; potassium pyrophosphate: 110-130g / L; The pH of the solution is between 10-11.
  • the bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.04 ⁇ m, and the copper plating temperature is 30-40 ° C; Then wash with water.
  • step S3 The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the surface of the bead wire is coated with a copper-nickel alloy layer with a thickness of 0.05 ⁇ m. ; Then wash with water.
  • step S4 The bead wire treated in step S3 is electroplated through a plating bath containing a copper-zinc alloy plating solution.
  • the copper plating temperature is 45-55 ° C, and the surface of the bead wire is coated with a copper-zinc alloy coating with a thickness of 0.05 ⁇ m. ; Then washing and drying treatment to obtain a bead wire with three multi-layer plating on its surface.
  • the travel speed of the bead wire in the three plating solutions is 380 m / min.
  • the prepared bead wire with multiple plating layers has three layers, the bottom layer is a copper-tin alloy coating, the middle is a copper-nickel alloy coating, and the surface layer is a copper-zinc alloy coating.
  • the copper-tin alloy plating layer is 0.04 ⁇ m, the copper-nickel alloy plating layer has a thickness of 0.05 ⁇ m, and the copper-zinc alloy plating layer has a thickness of 0.05 ⁇ m.
  • the experimental group and the control group of this embodiment both use GB 82 steel wire with a wire diameter of 1.2 mm.
  • the method for testing the adhesion force in this embodiment is the same as the method in embodiment 1.
  • test results were as follows: the adhesion between the control group and rubber was 1010N, the adhesion between the experimental group and rubber was 1075N, and the adhesion of the experimental group increased by 6.4%.
  • test results of the above three examples show that compared with the traditional copper alloy coating, the binding force of the bead wire with multi-plating is increased by at least 6%, and the bead wire with multi-plating can be applied to various high Various types of rubber, such as sulfur rubber and low sulfur rubber, have a wide range of applications.

Abstract

A tire bead wire having multiple platings and a plating method for platings thereof. The multiple platings on a surface of the tire bead wire are formed by three platings, wherein the three platings, from inside to outside, are a copper-tin alloy plating, a copper-nickel alloy plating, and a copper-zinc alloy plating, respectively. The thickness of the copper-tin alloy plating is 0.03 to 0.09 μm, the thickness of the copper-nickel alloy plating is 0.02 to 0.08 μm, the thickness of the copper-zinc alloy plating is 0.02 to 0.08 μm, and the total thickness of the three platings is 0.1 to 0.15 μm. The tire bead wire having multiple platings is applicable to multiple types of rubber, such as high sulfur rubber and low sulfur rubber, has a wide range of applications, and achieves improved binding strength when bound to rubber. The plating method for a plating thereof increases the speed of plating a plating on a surface of a tire bead wire, thereby improving production efficiency of a tire bead wire having multiple platings, and reducing production costs.

Description

一种带多元镀层的胎圈钢丝及其镀层施镀方法Bead wire with multiple plating layers and plating method thereof 技术领域Technical field
本发明涉及胎圈钢丝的生产领域，尤其涉及一种带多元镀层的胎圈钢丝及其镀层施镀方法。The invention relates to the field of bead wire production, in particular to a bead wire with multiple plating layers and a method for plating the same.
背景技术Background technique
由于胎圈钢丝在轮胎的使用过程中要承受极其复杂的交变负荷和冲击负荷，这要求胎圈钢丝必须与橡胶具有良好的粘合性能，反之，轮胎在使用过程中易产生钢丝圈松散、钢丝刺出，甚至会造成胎圈爆破等危害人身财产安全的事故。Because the bead wire must withstand extremely complex alternating and impact loads during the use of the tire, this requires that the bead wire must have good adhesion to the rubber. On the contrary, the tire tends to cause loose travellers during use, The wire puncture can even cause accidents such as bead blasting that endanger personal and property safety.
由于光面钢丝与橡胶的粘合性能极差, 因此必须在钢丝表面均匀覆盖镀层。镀铜后的胎圈钢丝与橡胶的黏合力主要体现为两种作用力，包括硫化后产生的硫化铜层与橡胶进行化学反应形成的化学黏合以及高极性的橡胶表面与钢丝表面形成的硫化亚铜薄膜之间的物理黏合，这两种形式黏合力共同作用使钢丝与橡胶之间进行良好黏合。根据橡胶制品的品种、运行速度、受力状态以及胶料配方, 胎圈钢丝表面镀层可以选择纯铜、锡青铜、黄铜和纯锌等单金属或二元合金。Because the adhesion between smooth steel wire and rubber is extremely poor, it is necessary to cover the surface of the steel wire with a uniform coating. The bonding force between the copper-plated bead wire and rubber is mainly reflected in two kinds of forces, including chemical bonding formed by the chemical reaction between the copper sulfide layer produced after vulcanization and rubber, and vulcanization formed by the highly polar rubber surface and the surface of the steel wire. The physical bonding between the cuprous films, these two forms of bonding forces work together to make a good bond between the steel wire and the rubber. According to the variety of rubber products, running speed, stress state, and rubber compound formula, the surface coating of the bead wire can be selected from single metals or binary alloys such as pure copper, tin bronze, brass, and pure zinc.
技术问题technical problem
钢丝与橡胶的粘合性能不仅取决于钢丝，与橡胶配方也有着密切关系。当橡胶配方一定时，影响粘合性能的主要因素是胎圈钢丝镀层成分和镀层厚度以及表面状况。由于不同轮胎的橡胶种类不同，生产时需要根据用户的橡胶类型与需求选择不同的镀层以适应相应橡胶特性，这就需要建设多条不同的镀铜生产线，或者是一条生产线配置多种镀铜装置，这会给工厂生产线的设置以及正常工艺安排带来了困难，并且生产成本的提高。The adhesion between steel wire and rubber is not only determined by the steel wire, but also closely related to the rubber formula. When the rubber formula is constant, the main factors affecting the adhesion performance are the bead wire coating composition, coating thickness, and surface condition. Due to the different rubber types of different tires, different plating layers need to be selected according to the rubber type and needs of the user to adapt to the corresponding rubber characteristics during production. This requires the construction of multiple different copper plating production lines, or a production line equipped with multiple copper plating devices. This will cause difficulties in setting up the factory production line and normal process arrangements, and increase production costs.
因此，现有技术有待提高。Therefore, the prior art needs to be improved.
技术解决方案Technical solutions
针对上述技术问题，本发明提供了适用于多种橡胶的带多元镀层的胎圈钢丝及其镀层施镀方法，以解决目前单一铜镀层或者合金镀层无法匹配多种轮胎橡胶的问题。In view of the above technical problems, the present invention provides a bead wire with multi-layer coating suitable for a variety of rubbers and a plating method thereof to solve the problem that a single copper or alloy coating cannot match a variety of tire rubbers at present.
本发明提供了一种带多元镀层的胎圈钢丝，其中，所述胎圈钢丝表面的多元镀层由三层镀层构成，其中，三层镀层从内向外分别为铜锡合金镀层、铜镍合金镀层和铜锌合金镀层。The invention provides a bead wire with multiple plating layers, wherein the multiple plating layer on the surface of the bead wire is composed of three layers, wherein the three layers are a copper-tin alloy coating and a copper-nickel alloy coating from the inside to the outside, respectively. And copper-zinc alloy coating.
所述的带多元镀层的胎圈钢丝，其中，所述铜锡合金镀层为0.03-0.09μm，铜镍合金镀层厚度为0.02-0.08μm，铜锌合金镀层厚度为0.02-0.08μm，三层镀层的总厚度为0.1-0.15μm。 The bead wire with multiple plating layers, wherein the copper-tin alloy coating is 0.03-0.09 μm, the thickness of the copper-nickel alloy coating is 0.02-0.08 μm, the thickness of the copper-zinc alloy coating is 0.02-0.08 μm, and the three-layer coating The total thickness is 0.1-0.15 μm.
所述的带多元镀层的胎圈钢丝，其中，所述铜锡合金镀层的锡含量为0.5%-12%，铜镍合金镀层的镍含量范围为50%-70%，铜锌合金镀层的锌含量为30%-40%。The bead wire with multiple plating layers, wherein the copper content of the copper-tin alloy coating layer is 0.5% -12%, the nickel content of the copper-nickel alloy coating layer is 50% -70%, and the copper content of the copper-zinc alloy coating layer is zinc. The content is 30% -40%.
如上所述的带多元镀层的胎圈钢丝的镀层施镀方法包括以下步骤：The plating method for a bead wire with multiple plating layers as described above includes the following steps:
S1：分别配置铜锡合金镀液、铜镍合金镀液和铜锌合金镀液；S1: Configure copper-tin alloy plating solution, copper-nickel alloy plating solution and copper-zinc alloy plating solution respectively;
S2：使胎圈钢丝直接经过盛装铜锡合金镀液的镀铜槽中进行化学镀铜，使胎圈钢丝表面镀上厚度为0.03-0.09μm的铜锡合金镀层；然后进行水洗；S2: The bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.03-0.09 μm; and then washed with water;
S3：使经过S2步骤处理的胎圈钢丝经过盛装铜镍合金镀液的电镀槽进行电镀，使胎圈钢丝表面镀上厚度为0.02-0.08μm的铜镍合金镀层；然后进行水洗；S3: The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution, and the surface of the bead wire is plated with a copper-nickel alloy layer having a thickness of 0.02-0.08 μm; and then washed with water;
S4：使经过S3步骤处理的胎圈钢丝经过盛装铜锌合金镀液的电镀槽进行电镀，使胎圈钢丝表面镀上厚度为0.02-0.08μm的铜锌合金镀层；然后进行水洗和干燥处理，获得表面镀有三层多元镀层的胎圈钢丝。S4: The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution, and the surface of the bead wire is plated with a copper-zinc alloy coating having a thickness of 0.02-0.08 μm; and then washed and dried. A bead wire having three multi-layer coatings on its surface was obtained.
所述的镀层施镀方法中，所述铜锡合金镀液包括以下浓度的组分：In the plating method, the copper-tin alloy plating solution includes the following components:
CuSO 4·5H 2O：10-16g/L； CuSO 4 · 5H 2 O: 10-16g / L;
SnSO 4：0.05-1.5g/L； SnSO 4 : 0.05-1.5g / L;
H 2 SO 4：10-16 g/L。 H 2 SO 4 : 10-16 g / L.
所述的镀层施镀方法中，所述的铜镍合金镀液包括以下质量浓度的组分：In the plating method, the copper-nickel alloy plating solution includes the following components in mass concentration:
CuSO 4·5H 2O：7-13g/L； CuSO 4 · 5H 2 O: 7-13g / L;
NiSO 4·6H 2O：15-25g/L； NiSO 4 · 6H 2 O: 15-25g / L;
焦磷酸钾：110-130g/L；Potassium pyrophosphate: 110-130g / L;
其中，镀液pH值为 8.5-9.5。Among them, the pH of the plating solution is 8.5-9.5.
所述的镀层施镀方法中，所述的铜锌合金镀液包括以下质量浓度的组分：In the plating method, the copper-zinc alloy plating solution includes the following components in mass concentration:
CuSO 4·5H 2O：10-20g/L； CuSO 4 · 5H 2 O: 10-20g / L;
ZnSO 4·7H 2O：11-21g/L； ZnSO 4 · 7H 2 O: 11-21g / L;
焦磷酸钾：110-130g/L；Potassium pyrophosphate: 110-130g / L;
其中，镀液pH值在 10-11。Among them, the pH value of the plating solution is 10-11.
所述的镀层施镀方法中，S2步骤的镀铜温度为30-40℃，S3步骤镀铜温度都为45-55℃，S4步骤镀铜温度为45-55℃。In the plating method, the copper plating temperature in step S2 is 30-40 ° C, the copper plating temperature in step S3 is 45-55 ° C, and the copper plating temperature in step S4 is 45-55 ° C.
所述的镀层施镀方法中，胎圈钢丝在三种镀液中的行进速度为350-400m/min。In the plating method, the travel speed of the bead wire in the three plating solutions is 350-400 m / min.
有益效果Beneficial effect
本发明提供的带多元镀层的胎圈钢丝及其镀层施镀方法具有以下有益效果：The bead wire with multiple plating layers and the plating method thereof provided by the present invention have the following beneficial effects:
1. 本发明提供的多元镀层专用于胎圈钢丝表面镀铜处理，带多元镀层的胎圈钢丝可以适用于高硫橡胶、低硫橡胶等多种类型的橡胶，适用面广，极大地简化了工厂生产线的设置以及降低了生产成本；1. The multi-layer plating provided by the present invention is specially used for copper plating on the surface of the bead wire. The bead wire with multi-layer plating can be applied to various types of rubber such as high sulfur rubber and low sulfur rubber, which has a wide range of applications and greatly simplifies. Set up factory production lines and reduce production costs;
2. 相较于传统单一铜合金镀层，由内外设置的铜锡合金镀层、铜镍合金镀层和铜锌合金镀层组成的多元镀层将胎圈钢丝与橡胶的结合力提高6%以上。2. Compared with the traditional single copper alloy coating, the multi-layer coating consisting of copper-tin alloy coating, copper-nickel alloy coating and copper-zinc alloy coating provided inside and outside improves the binding force of the bead wire and rubber by more than 6%.
3.本发明提供的镀层施镀方法使胎圈钢丝表面镀层的施镀速度得到显著提升，胎圈钢丝施镀过程中的行进速度提高到350-400m/min，是传统单一镀层行进速度的1.5-2倍，从而大幅度提高了所述带多元镀层的胎圈钢丝的生产效率，降低了生产成本。3. The plating method provided by the present invention significantly improves the plating speed of the bead wire surface coating, and the traveling speed during the bead wire plating process is increased to 350-400m / min, which is 1.5 times that of the traditional single plating. -2 times, thereby greatly improving the production efficiency of the bead wire with multi-layer plating and reducing the production cost.
本发明的最佳实施方式Best Mode of the Invention
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work fall into the protection scope of the present invention.
本发明提供了一种带多元镀层的胎圈钢丝，其中，所述胎圈钢丝表面的多元镀层由三层镀层构成，其中，三层镀层从内向外分别为铜锡合金镀层、铜镍合金镀层和铜锌合金镀层。The invention provides a bead wire with multiple plating layers, wherein the multiple plating layer on the surface of the bead wire is composed of three layers, wherein the three layers are a copper-tin alloy coating and a copper-nickel alloy coating from the inside to the outside, respectively. And copper-zinc alloy coating.
其中，位于最内层的铜锡合金镀层起基地作用，位于中层的铜镍合金镀层作为过渡层，起到防腐作用，位于最外层的铜锌合金镀层主要起到与橡胶黏合的作用。铜锡合金镀层和铜镍合金镀层配合铜锌合金镀层共同作用进一步提高多元镀层与橡胶的黏合力，也提高了胎圈钢丝的防腐蚀、防锈性能。Among them, the copper-tin alloy plating layer in the innermost layer serves as a base, and the copper-nickel alloy plating layer in the middle layer serves as a transition layer to prevent corrosion. The copper-zinc alloy plating layer in the outermost layer mainly plays a role of bonding with rubber. The combination of copper-tin alloy coating and copper-nickel alloy coating and copper-zinc alloy coating further improves the adhesion between the multi-layer coating and rubber, and also improves the anti-corrosion and rust-proof performance of the bead wire.
优选地，所述铜锡合金镀层为0.03-0.09μm，铜镍合金镀层厚度为0.02-0.08μm ，铜锌合金镀层厚度为0.02-0.08μm，三层镀层的总厚度为0.1-0.15μm，并且三层镀层的总厚度为0.1-0.15μm。上述设置的多元镀层的厚度最佳，不仅使多元镀层与多种橡胶黏合力得到极大提高，并且使胎圈钢丝保持正常的机械性能，且不易出现锈化现象。而上述多元镀层的过厚会引起镀层界面的内聚力的破坏，导致镀层间结合性减弱以及多元镀层与橡胶的黏合力的下降；多元镀层的过薄会导致各镀层的厚薄不均、镀层的防锈能力下降，镀层的综合性能下降。Preferably, the copper-tin alloy coating is 0.03-0.09 μm, the thickness of the copper-nickel alloy coating is 0.02-0.08 μm, the thickness of the copper-zinc alloy coating is 0.02-0.08 μm, and the total thickness of the three-layer coating is 0.1-0.15 μm, and The total thickness of the three plating layers is 0.1-0.15 μm. The thickness of the multi-plated coating provided above is optimal, which not only greatly improves the adhesion between the multi-plated coating and various rubbers, but also maintains the normal mechanical properties of the bead wire, and is less prone to rusting. The excessive thickness of the above-mentioned multi-layer plating will cause the cohesion of the plating interface to be destroyed, resulting in a decrease in the adhesion between the plating layers and a decrease in the adhesion between the multi-layer plating and the rubber. The rust ability is reduced, and the comprehensive performance of the coating is reduced.
优选地，所述铜锡合金镀层的锡含量为0.5%-12%，铜镍合金镀层的镍含量范围为50%-70%，铜锌合金镀层的锌含量为30%-40%。这样设置配合多元镀层厚度和位置分布的设置使多元合金镀层的综合性能好，与多种橡胶（高硫橡胶、低硫橡胶等）的黏合力大，适用范围广。Preferably, the tin content of the copper-tin alloy coating is 0.5% -12%, the nickel content of the copper-nickel alloy coating is in the range of 50% -70%, and the copper content of the copper-zinc alloy coating is 30% -40%. The setting in accordance with the thickness and position distribution of the multi-layer coating makes the comprehensive performance of the multi-layer alloy coating good, and it has a large adhesive force with various rubbers (high sulfur rubber, low sulfur rubber, etc.), and has a wide application range.
上述带多元镀层的胎圈钢丝的镀层施镀方法包括以下具体步骤：The plating method for the above-mentioned multi-plated bead wire includes the following specific steps:
S1：按照以下配方分别配置铜锡合金镀液、铜镍合金镀液和铜锌合金镀液；其中，所述铜锡合金镀液包括以下浓度的组分：S1: A copper-tin alloy plating solution, a copper-nickel alloy plating solution, and a copper-zinc alloy plating solution are respectively configured according to the following formula; wherein the copper-tin alloy plating solution includes the following concentrations of components:
CuSO 4·5H 2O：10-16g/L； CuSO 4 · 5H 2 O: 10-16g / L;
SnSO 4：0.05-1.5g/L； SnSO 4 : 0.05-1.5g / L;
H 2 SO 4：10-16 g/L。 H 2 SO 4 : 10-16 g / L.
所述的铜镍合金镀液包括以下质量浓度的组分：The copper-nickel alloy plating solution includes the following components in mass concentration:
CuSO 4·5H 2O：7-13g/L； CuSO 4 · 5H 2 O: 7-13g / L;
NiSO 4·6H 2O：15-25g/L； NiSO 4 · 6H 2 O: 15-25g / L;
焦磷酸钾：110-130g/L；Potassium pyrophosphate: 110-130g / L;
其中，镀液pH值为 8.5-9.5。Among them, the pH of the plating solution is 8.5-9.5.
所述的铜锌合金镀液包括以下质量浓度的组分：The copper-zinc alloy plating solution includes the following components in mass concentration:
CuSO 4·5H 2O：10-20g/L； CuSO 4 · 5H 2 O: 10-20g / L;
ZnSO 4·7H 2O：11-21g/L； ZnSO 4 · 7H 2 O: 11-21g / L;
焦磷酸钾：110-130g/L；Potassium pyrophosphate: 110-130g / L;
其中，镀液pH值在 10-11。Among them, the pH value of the plating solution is 10-11.
上述三种镀液以水为溶剂进行配置。The three types of plating solutions described above are arranged using water as a solvent.
上述三种镀液的配置方法为：在相应的化镀槽中加入纯净水，接着分别加入定量的各个组分，混合均匀，调节PH值后，并将镀液分别升温至相应的镀铜温度。The three methods of configuring the above plating solutions are: adding purified water to the corresponding plating baths, and then adding a fixed amount of each component, mixing them uniformly, adjusting the pH value, and heating the plating solutions to the corresponding copper plating temperatures. .
上述三种镀层的配方的原料种类少，易收集，配置方法简单，不需要复杂的实验设备，操作简单；并且上述配方制备的三种镀液形成镀层速度快，在钢丝表面形成的多元镀层稳定，与橡胶的结合能力强，使用范围广。The three types of coatings mentioned above have few types of raw materials, are easy to collect, simple to configure, do not require complicated experimental equipment, and are easy to operate. In addition, the three types of plating solutions prepared by the above formulas have fast formation of coatings and stable multi-layer coatings on the surface of steel wires. , Strong binding ability with rubber, wide range of use.
S2：使胎圈钢丝直接经过盛装铜锡合金镀液的镀铜槽中进行化学镀铜，使胎圈钢丝表面镀上厚度为0.03-0.09μm的铜锡合金镀层，镀铜温度为30-40℃；然后进行水洗。S2: The bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the bead wire surface is plated with a copper-tin alloy coating having a thickness of 0.03-0.09 μm, and the copper plating temperature is 30-40 ° C; then washed with water.
S3：使经过S2步骤处理的胎圈钢丝经过盛装铜镍合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.02-0.08μm的铜镍合金镀层；然后进行水洗。S3: The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution. The copper plating temperature is 45-55 ° C, and the bead wire surface is plated with copper-nickel having a thickness of 0.02-0.08 μm. Alloy plating; then washed with water.
S4：使经过S3步骤处理的胎圈钢丝经过盛装铜锌合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.02-0.08μm的铜锌合金镀层；然后进行水洗和干燥处理，获得表面镀有三层多元镀层的胎圈钢丝。S4: The bead wire treated in step S3 is electroplated through a plating bath containing a copper-zinc alloy plating solution. The copper plating temperature is 45-55 ° C, and the surface of the bead wire is coated with copper-zinc with a thickness of 0.02-0.08 μm. Alloy plating; and then washed and dried to obtain a bead wire with three multi-layer plating on its surface.
其中，胎圈钢丝在三种镀液中的行进速度为350-400m/min。与传统镀线速度200-300m/min相比，胎圈钢丝化镀的行进速度提升了1.5-2倍。由于各镀液在胎圈钢丝表面形成镀层速度快，上述胎圈钢丝的行进速度不仅能满足化镀要求，并且大幅度提高了工作效率，降低了化镀的生产成本。Among them, the travel speed of the bead wire in the three plating solutions is 350-400m / min. Compared with the traditional plating speed of 200-300m / min, the travel speed of bead wire plating is increased by 1.5-2 times. Because each plating solution forms a plating layer on the surface of the bead wire at a high speed, the travel speed of the bead wire can not only meet the requirements of electroless plating, but also greatly improve the work efficiency and reduce the production cost of electroless plating.
实施例1Example 1
本实施例提供一种带多元镀层的胎圈钢丝的镀层施镀方法，具体步骤如下：This embodiment provides a plating method for a bead wire with multiple plating layers. The specific steps are as follows:
S1：分别按照以下配方分别配置铜锡合金镀液、铜镍合金镀液和铜锌合金镀液；S1: Configure copper-tin alloy plating solution, copper-nickel alloy plating solution and copper-zinc alloy plating solution according to the following formulas, respectively;
其中，所述铜锡合金镀液包括以下浓度的组分：CuSO 4·5H 2O：16g/L； Wherein, the copper-tin alloy plating solution includes the following components: CuSO 4 · 5H 2 O: 16g / L;
SnSO 4：1.5g/L；H 2 SO 4：10-16 g/L。 SnSO 4 : 1.5 g / L; H 2 SO 4 : 10-16 g / L.
所述的铜镍合金镀液包括以下质量浓度的组分：CuSO 4·5H 2O：7g/L； The copper-nickel alloy plating solution includes the following components in mass concentration: CuSO 4 · 5H 2 O: 7g / L;
NiSO 4·6H 2O：15g/L；焦磷酸钾：110-130g/L；其中，镀液pH值为8.5-9.5。 NiSO 4 · 6H 2 O: 15 g / L; potassium pyrophosphate: 110-130 g / L; wherein the pH of the plating solution is 8.5-9.5.
所述的铜锌合金镀液包括以下质量浓度的组分：CuSO 4·5H 2O：10g/L；ZnSO 4·7H 2O：11g/L；焦磷酸钾：110-130g/L ；其中，镀液pH值在 10-11。 The copper-zinc alloy plating solution includes the following components in mass concentration: CuSO 4 · 5H 2 O: 10g / L; ZnSO 4 · 7H 2 O: 11g / L; potassium pyrophosphate: 110-130g / L; wherein, The pH of the plating solution is 10-11.
S2：将胎圈钢丝直接经过盛装铜锡合金镀液的镀铜槽中进行化学镀铜，使胎圈钢丝表面镀上厚度为0.09μm的铜锡合金镀层，镀铜温度为30-40℃；然后进行水洗。S2: The bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.09 μm, and the copper plating temperature is 30-40 ° C; Then wash with water.
S3：使经过S2步骤处理的胎圈钢丝经过盛装铜镍合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.02μm的铜镍合金镀层；然后进行水洗。S3: The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution. The copper plating temperature is 45-55 ° C, and the surface of the bead wire is plated with a copper-nickel alloy layer with a thickness of 0.02 μm. ; Then wash with water.
S4：使经过S3步骤处理的胎圈钢丝经过盛装铜锌合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.02μm的铜锌合金镀层；然后进行水洗和干燥处理，获得表面镀有三层多元镀层的胎圈钢丝。S4: The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution. The copper plating temperature is 45-55 ° C, and the bead wire surface is coated with a copper-zinc alloy coating with a thickness of 0.02 μm. ; Then washing and drying treatment to obtain a bead wire with three multi-layer plating on its surface.
其中，胎圈钢丝在三种镀液中的行进速度为350m/min。Among them, the travel speed of the bead wire in the three plating solutions is 350 m / min.
制备得到的带多元镀层的胎圈钢丝具有三层镀层，底层为铜锡合金镀层，中间为铜镍合金镀层，表层为铜锌合金镀层。其中铜锡合金镀层为0.09μm，铜镍合金镀层厚度为0.02μm ，铜锌合金镀层厚度为0.02μm。The prepared bead wire with multiple plating layers has three layers, the bottom layer is a copper-tin alloy coating, the middle is a copper-nickel alloy coating, and the surface layer is a copper-zinc alloy coating. The copper-tin alloy coating is 0.09 μm, the thickness of the copper-nickel alloy coating is 0.02 μm, and the thickness of the copper-zinc alloy coating is 0.02 μm.
黏合力测试Adhesion test
根据国家标准GB／T 14450-2016中黏合力的检测方法对上述胎圈钢丝与硫化橡胶的黏合力进行测试。本实施例采用的钢丝为国标72钢，线径为0.96mm。以传统的镀有相同厚度单一铜合金镀层的同型号钢丝作为对照组，本实施例的带有多远镀层的胎圈钢丝作为实验组，分别对两组胎圈钢丝进行与硫化橡胶的黏合力测试。According to the national standard GB / T 14450-2016 adhesion test method, test the adhesion of the bead wire and vulcanized rubber. The steel wire used in this embodiment is national standard 72 steel, and the wire diameter is 0.96 mm. A conventional steel wire of the same type coated with a single copper alloy coating of the same thickness was used as a control group, and the bead wire with a multi-layer coating in this embodiment was used as an experimental group. The adhesion of the two sets of bead wires to vulcanized rubber was tested. .
具体测试方法为：将炼制均匀的胶料放入硫化模具中，并将实验组和一个对照组分别放置于胶料中间，用平板硫化机进行硫化，胶料冷却后通过英斯特朗拉力机将三个实验组的胎圈钢丝从胶料中拔出得到的最大力为黏合力。 The specific test method is: put the refined homogeneous rubber compound into a vulcanization mold, and place the experimental group and a control group in the middle of the rubber compound respectively, vulcanize with a flat plate vulcanizer, and cool the rubber compound through Instron pull force The maximum force obtained by the machine when the bead wire of the three experimental groups was pulled out of the rubber compound was the adhesion force.
测试结果为：对照组与橡胶的黏合力为1020N，实验组与橡胶的黏合力为1095N，实验组的黏合力提高了7.3%。The test results were as follows: the adhesion between the control group and rubber was 1020N, the adhesion between the experimental group and rubber was 1095N, and the adhesion of the experimental group increased by 7.3%.
本发明的实施方式Embodiments of the invention
实施例2Example 2
本实施例提供一种带多元镀层的胎圈钢丝的镀层施镀方法，具体步骤如下：This embodiment provides a plating method for a bead wire with multiple plating layers. The specific steps are as follows:
S1：分别按照以下配方分别配置铜锡合金镀液、铜镍合金镀液和铜锌合金镀液；S1: Configure copper-tin alloy plating solution, copper-nickel alloy plating solution and copper-zinc alloy plating solution according to the following formulas, respectively;
其中，所述铜锡合金镀液包括以下浓度的组分：CuSO 4·5H 2O：10g/L； Wherein, the copper-tin alloy plating solution includes the following components: CuSO 4 · 5H 2 O: 10 g / L;
SnSO 4：0.05g/L；H 2 SO 4：10-16 g/L。 SnSO 4 : 0.05 g / L; H 2 SO 4 : 10-16 g / L.
所述的铜镍合金镀液包括以下质量浓度的组分：CuSO 4·5H 2O：13g/L； The copper-nickel alloy plating solution includes the following components in mass concentration: CuSO 4 · 5H 2 O: 13 g / L;
NiSO 4·6H 2O：25g/L；焦磷酸钾：110-130g/L；其中，镀液pH值为8.5-9.5。 NiSO 4 · 6H 2 O: 25 g / L; potassium pyrophosphate: 110-130 g / L; wherein the pH of the plating solution is 8.5-9.5.
所述的铜锌合金镀液包括以下质量浓度的组分：CuSO 4·5H 2O：10g/L；ZnSO 4·7H 2O：11g/L；焦磷酸钾：110-130g/L；其中，镀液pH值在 10-11。 The copper-zinc alloy plating solution includes the following components in mass concentration: CuSO 4 · 5H 2 O: 10g / L; ZnSO 4 · 7H 2 O: 11g / L; potassium pyrophosphate: 110-130g / L; The pH of the plating solution is 10-11.
S2：使胎圈钢丝直接经过盛装铜锡合金镀液的镀铜槽中进行化学镀铜，使胎圈钢丝表面镀上厚度为0.03μm的铜锡合金镀层，镀铜温度为30-40℃；然后进行水洗。S2: The bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the bead wire surface is plated with a copper-tin alloy coating having a thickness of 0.03 μm, and the copper plating temperature is 30-40 ° C; Then wash with water.
S3：使经过S2步骤处理的胎圈钢丝经过盛装铜镍合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.08μm的铜镍合金镀层；然后进行水洗。S3: The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution. The copper plating temperature is 45-55 ° C, and the surface of the bead wire is plated with a copper-nickel alloy layer with a thickness of 0.08 μm. ; Then wash with water.
S4：使经过S3步骤处理的胎圈钢丝经过盛装铜锌合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.02μm的铜锌合金镀层；然后进行水洗和干燥处理，获得表面镀有三层多元镀层的胎圈钢丝。S4: The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution. The copper plating temperature is 45-55 ° C, and the bead wire surface is coated with a copper-zinc alloy coating with a thickness of 0.02 μm. ; Then washing and drying treatment to obtain a bead wire with three multi-layer plating on its surface.
其中，胎圈钢丝在三种镀液中的行进速度为400m/min。Among them, the travel speed of the bead wire in the three plating solutions is 400 m / min.
制备得到的带多元镀层的胎圈钢丝，具有三层镀层，底层为铜锡合金镀层，中间为铜镍合金镀层，表层为铜锌合金镀层。其中，铜锡合金镀层为0.03μm，铜镍合金镀层厚度为0.08μm ，铜锌合金镀层厚度为0.02μm。The prepared bead wire with multiple plating layers has three layers, the bottom layer is a copper-tin alloy coating, the middle is a copper-nickel alloy coating, and the surface layer is a copper-zinc alloy coating. Among them, the thickness of the copper-tin alloy coating is 0.03 μm, the thickness of the copper-nickel alloy coating is 0.08 μm, and the thickness of the copper-zinc alloy coating is 0.02 μm.
黏合力测试Adhesion test
本实施例的实验组和对照组都采用国标80钢的钢丝，线径为1.2mm。本实施例的黏合力测试方法与实施例1的方法相同。       The experimental group and the control group of this embodiment both use GB 80 steel wire with a wire diameter of 1.2 mm. The method for testing the adhesion force in this embodiment is the same as the method in embodiment 1.
测试结果为：对照组与橡胶的黏合力为1015N，实验组与橡胶的黏合力为1090N，实验组的黏合力提高了7.8%。The test results were as follows: the adhesion between the control group and rubber was 1015N, the adhesion between the experimental group and rubber was 1090N, and the adhesion of the experimental group increased by 7.8%.
实施例3Example 3
本实施例提供一种带多元镀层的胎圈钢丝的镀层施镀方法，具体步骤如下：This embodiment provides a plating method for a bead wire with multiple plating layers. The specific steps are as follows:
S1：分别按照以下配方分别配置铜锡合金镀液、铜镍合金镀液和铜锌合金镀液；S1: Configure copper-tin alloy plating solution, copper-nickel alloy plating solution and copper-zinc alloy plating solution according to the following formulas, respectively;
其中，所述铜锡合金镀液包括以下浓度的组分：CuSO 4·5H 2O：13g/L； Wherein, the copper-tin alloy plating solution includes the following components: CuSO 4 · 5H 2 O: 13g / L;
SnSO 4：0.1g/L；H 2 SO 4：10-16 g/L。 SnSO 4 : 0.1 g / L; H 2 SO 4 : 10-16 g / L.
所述的铜镍合金镀液包括以下质量浓度的组分：CuSO 4·5H 2O：10g/L； The copper-nickel alloy plating solution includes the following components in mass concentration: CuSO 4 · 5H 2 O: 10 g / L;
NiSO 4·6H 2O：20g/L；焦磷酸钾：110-130g/L；其中，镀液pH值为8.5-9.5。 NiSO 4 · 6H 2 O: 20 g / L; potassium pyrophosphate: 110-130 g / L; wherein the pH of the plating solution is 8.5-9.5.
所述的铜锌合金镀液包括以下质量浓度的组分：CuSO 4·5H 2O：15g/L；ZnSO4·7H 2O：16g/L；焦磷酸钾：110-130g/L； 其中，镀液pH值在 10-11。 The copper-zinc alloy plating solution includes the following components in mass concentration: CuSO 4 · 5H 2 O: 15g / L; ZnSO4 · 7H 2 O: 16g / L; potassium pyrophosphate: 110-130g / L; The pH of the solution is between 10-11.
S2：使胎圈钢丝直接经过盛装铜锡合金镀液的镀铜槽中进行化学镀铜，使胎圈钢丝表面镀上厚度为0.04μm的铜锡合金镀层，镀铜温度为30-40℃；然后进行水洗。S2: The bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.04 μm, and the copper plating temperature is 30-40 ° C; Then wash with water.
S3：使经过S2步骤处理的胎圈钢丝经过盛装铜镍合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.05μm的铜镍合金镀层；然后进行水洗。S3: The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution. The copper plating temperature is 45-55 ° C, and the surface of the bead wire is coated with a copper-nickel alloy layer with a thickness of 0.05 μm. ; Then wash with water.
S4：使经过S3步骤处理的胎圈钢丝经过盛装铜锌合金镀液的电镀槽进行电镀，镀铜温度都为45-55℃，使胎圈钢丝表面镀上厚度为0.05μm的铜锌合金镀层；然后进行水洗和干燥处理，获得表面镀有三层多元镀层的胎圈钢丝。S4: The bead wire treated in step S3 is electroplated through a plating bath containing a copper-zinc alloy plating solution. The copper plating temperature is 45-55 ° C, and the surface of the bead wire is coated with a copper-zinc alloy coating with a thickness of 0.05 μm. ; Then washing and drying treatment to obtain a bead wire with three multi-layer plating on its surface.
其中，胎圈钢丝在三种镀液中的行进速度为380m/min。Among them, the travel speed of the bead wire in the three plating solutions is 380 m / min.
制备得到的带多元镀层的胎圈钢丝，具有三层镀层，底层为铜锡合金镀层，中间为铜镍合金镀层，表层为铜锌合金镀层。其中，铜锡合金镀层为0.04μm，铜镍合金镀层厚度为0.05μm ，铜锌合金镀层厚度为0.05μm。The prepared bead wire with multiple plating layers has three layers, the bottom layer is a copper-tin alloy coating, the middle is a copper-nickel alloy coating, and the surface layer is a copper-zinc alloy coating. The copper-tin alloy plating layer is 0.04 μm, the copper-nickel alloy plating layer has a thickness of 0.05 μm, and the copper-zinc alloy plating layer has a thickness of 0.05 μm.
黏合力测试Adhesion test
本实施例的实验组和对照组都采用国标82钢的钢丝，线径为1.2mm。本实施例的黏合力测试方法与实施例1的方法相同。       The experimental group and the control group of this embodiment both use GB 82 steel wire with a wire diameter of 1.2 mm. The method for testing the adhesion force in this embodiment is the same as the method in embodiment 1.
测试结果为：对照组与橡胶的黏合力为1010N，实验组与橡胶的黏合力为1075N，实验组的黏合力提高了6.4%。The test results were as follows: the adhesion between the control group and rubber was 1010N, the adhesion between the experimental group and rubber was 1075N, and the adhesion of the experimental group increased by 6.4%.
工业实用性Industrial applicability
通过上述三个实施例的测试结果表明：与传统铜合金镀层相比，带多元镀层的胎圈钢丝与橡胶的结合力提高至少6%，并且带多元镀层的胎圈钢丝能适用于各种高硫橡胶、低硫橡胶等多种类型的橡胶，适用范围广。The test results of the above three examples show that compared with the traditional copper alloy coating, the binding force of the bead wire with multi-plating is increased by at least 6%, and the bead wire with multi-plating can be applied to various high Various types of rubber, such as sulfur rubber and low sulfur rubber, have a wide range of applications.
可以理解的是，对本领域普通技术人员来说，可以根据本发明的技术方案及本发明构思加以等同替换或改变，而所有这些改变或替换都应属于本发明所附的权利要求的保护范围。It can be understood that for a person of ordinary skill in the art, equivalent replacements or changes can be made according to the technical solution of the present invention and the inventive concept, and all these changes or replacements should fall within the protection scope of the claims attached to the present invention.

Claims (9)

  1. 一种带多元镀层的胎圈钢丝，其特征在于，所述胎圈钢丝表面的多元镀层由三层镀层构成，其中，三层镀层从内向外分别为铜锡合金镀层、铜镍合金镀层和铜锌合金镀层。A bead wire with multiple plating layers is characterized in that the multiple plating layer on the surface of the bead wire is composed of three layers of coatings, wherein the three layers of coating are copper-tin alloy coating, copper-nickel alloy coating, and copper from the inside to the outside, respectively. Zinc alloy coating.
  2. 根据权利要求1所述的带多元镀层的胎圈钢丝，其特征在于，所述铜锡合金镀层为0.03-0.09μm，铜镍合金镀层厚度为0.02-0.08μm ，铜锌合金镀层厚度为0.02-0.08μm，三层镀层的总厚度为0.1-0.15μm。The bead wire with multiple coatings according to claim 1, wherein the copper-tin alloy coating is 0.03-0.09 μm, the copper-nickel alloy coating is 0.02-0.08 μm, and the copper-zinc alloy coating is 0.02- 0.08 μm, the total thickness of the three plating layers is 0.1-0.15 μm.
  3. 根据权利要求2所述的带多元镀层的胎圈钢丝，其特征在于，所述铜锡合金镀层的锡含量为0.5%-12%，铜镍合金镀层的镍含量范围为50%-70%，铜锌合金镀层的锌含量为30%-40%。The bead wire with a multi-layer coating according to claim 2, wherein the tin content of the copper-tin alloy coating is 0.5% -12%, and the nickel content of the copper-nickel alloy coating ranges from 50% to 70%. The zinc content of the copper-zinc alloy coating is 30% -40%.
  4. 如权利要求1所述的带多元镀层的胎圈钢丝的镀层施镀方法，其特征在于，包括以下步骤：The method for plating a bead wire with multiple plating layers according to claim 1, further comprising the following steps:
    S1：分别配置铜锡合金镀液、铜镍合金镀液和铜锌合金镀液；S1: Configure copper-tin alloy plating solution, copper-nickel alloy plating solution and copper-zinc alloy plating solution respectively;
    S2：使胎圈钢丝直接经过盛装铜锡合金镀液的镀铜槽中进行化学镀铜，使胎圈钢丝表面镀上厚度为0.03-0.09μm的铜锡合金镀层；然后进行水洗；S2: The bead wire is directly passed through a copper plating tank containing a copper-tin alloy plating solution for chemical copper plating, and the surface of the bead wire is plated with a copper-tin alloy coating having a thickness of 0.03-0.09 μm; and then washed with water;
    S3：使经过S2步骤处理的胎圈钢丝经过盛装铜镍合金镀液的电镀槽进行电镀，使胎圈钢丝表面镀上厚度为0.02-0.08μm的铜镍合金镀层；然后进行水洗；S3: The bead wire treated in step S2 is electroplated through a plating bath containing a copper-nickel alloy plating solution, and the surface of the bead wire is plated with a copper-nickel alloy layer having a thickness of 0.02-0.08 μm; and then washed with water;
    S4：使经过S3步骤处理的胎圈钢丝经过盛装铜锌合金镀液的电镀槽进行电镀，使胎圈钢丝表面镀上厚度为0.02-0.08μm的铜锌合金镀层；然后进行水洗和干燥处理，获得表面镀有三层多元镀层的胎圈钢丝。S4: The bead wire treated in step S3 is electroplated through an electroplating tank containing a copper-zinc alloy plating solution, and the surface of the bead wire is plated with a copper-zinc alloy coating having a thickness of 0.02-0.08 μm; and then washed and dried. A bead wire having three multi-layer coatings on its surface was obtained.
  5. 如权利要求4所述的镀层施镀方法，其特征在于，所述铜锡合金镀液包括以下浓度的组分：The method of claim 4, wherein the copper-tin alloy plating solution comprises the following components:
    CuSO 4 5H 2O：10-16g/L； CuSO 4 5H 2 O: 10-16g / L;
    SnSO 4：0.05-1.5g/L； SnSO 4 : 0.05-1.5g / L;
    H 2SO 4：10-16 g/L。 H 2 SO 4 : 10-16 g / L.
  6. 根据权利要求4所述的镀层施镀方法，其特征在于，所述的铜镍合金镀液包括以下质量浓度的组分：The method of claim 4, wherein the copper-nickel alloy plating solution includes the following components in mass concentration:
    CuSO 4 5H 2O：7-13g/L； CuSO 4 5H 2 O: 7-13g / L;
    NiSO 4 6H 2O：15-25g/L； NiSO 4 6H 2 O: 15-25g / L;
    焦磷酸钾：110-130g/L；Potassium pyrophosphate: 110-130g / L;
    其中，镀液pH值为 8.5-9.5。Among them, the pH of the plating solution is 8.5-9.5.
  7. 根据权利要求4所述的镀层施镀方法，其特征在于，所述的铜锌合金镀液包括以下质量浓度的组分：The method according to claim 4, wherein the copper-zinc alloy plating solution comprises the following components in a mass concentration:
    CuSO 4 5H 2O：10-20g/L； CuSO 4 5H 2 O: 10-20g / L;
    ZnSO 4 7H 2O：11-21g/L； ZnSO 4 7H 2 O: 11-21g / L;
    焦磷酸钾：110-130g/L；Potassium pyrophosphate: 110-130g / L;
    其中，镀液pH值在 10-11。Among them, the pH value of the plating solution is 10-11.
  8. 根据权利要求4所述的镀层施镀方法，其特征在于，S2步骤的镀铜温度为30-40℃，S3步骤的镀铜温度为45-55℃，S4步骤的镀铜温度为45-55℃。The plating method according to claim 4, wherein the copper plating temperature in step S2 is 30-40 ° C, the copper plating temperature in step S3 is 45-55 ° C, and the copper plating temperature in step S4 is 45-55 ℃.
  9. 根据权利要求4-8中任一项所述的镀层施镀方法，其特征在于，胎圈钢丝在三种镀液中的行进速度为350-400m/min。The plating method according to any one of claims 4 to 8, wherein the travel speed of the bead wire in the three plating solutions is 350-400 m / min.
PCT/CN2018/101709 2018-08-13 2018-08-22 Tire bead wire having multiple platings and plating method for platings thereof WO2020034241A1 (en)

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Publication number Priority date Publication date Assignee Title
CN114075682A (en) * 2020-08-13 2022-02-22 唐文海 Process for chemically plating steel spring part

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101316960A (en) * 2005-12-01 2008-12-03 住友橡胶工业株式会社 Metallic cord, rubber/cord composite object, and pneumatic tire obtained using the same
JP2011219836A (en) * 2010-04-13 2011-11-04 Nippon Steel Corp Extra fine plated steel wire having excellent adhesiveness to rubber
CN102517581A (en) * 2011-12-27 2012-06-27 山东大业股份有限公司 High-strength tin-plated bronze tire bead steel wire and preparation method thereof
CN104487631A (en) * 2012-07-24 2015-04-01 贝卡尔特公司 A steel cord for rubber reinforcement with selectively brass coated filaments
CN105568264A (en) * 2015-12-30 2016-05-11 江苏兴达钢帘线股份有限公司 Chemical plating method of tire bead steel wire
CN107824630A (en) * 2017-10-23 2018-03-23 江苏兴达钢帘线股份有限公司 A kind of metal wire, its manufacture method and tire

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY111621A (en) * 1993-12-16 2000-09-27 Kiyokawa Plating Ind Co Ltd Method for producing metal film resistor
US20090056847A1 (en) * 2004-07-01 2009-03-05 Pirelli Pneumatici S.P.A. Studded tire
FR2946366B1 (en) * 2009-06-03 2011-12-02 Michelin Soc Tech THREE-LAYER CABLE, IN SITU GUM, FOR PNEUMATIC CARCASS REINFORCEMENT.
CN103924225A (en) * 2014-01-23 2014-07-16 江苏兴达钢帘线股份有限公司 High tin bronze plating solution for chemical plating of surface of tempered bead wire, and its chemical dip plating method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101316960A (en) * 2005-12-01 2008-12-03 住友橡胶工业株式会社 Metallic cord, rubber/cord composite object, and pneumatic tire obtained using the same
JP2011219836A (en) * 2010-04-13 2011-11-04 Nippon Steel Corp Extra fine plated steel wire having excellent adhesiveness to rubber
CN102517581A (en) * 2011-12-27 2012-06-27 山东大业股份有限公司 High-strength tin-plated bronze tire bead steel wire and preparation method thereof
CN104487631A (en) * 2012-07-24 2015-04-01 贝卡尔特公司 A steel cord for rubber reinforcement with selectively brass coated filaments
CN105568264A (en) * 2015-12-30 2016-05-11 江苏兴达钢帘线股份有限公司 Chemical plating method of tire bead steel wire
CN107824630A (en) * 2017-10-23 2018-03-23 江苏兴达钢帘线股份有限公司 A kind of metal wire, its manufacture method and tire

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