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WO2024188594A1 - Composite de caoutchouc et procédé de fabrication du composite de caoutchouc - Google Patents

Composite de caoutchouc et procédé de fabrication du composite de caoutchouc Download PDF

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Publication number
WO2024188594A1
WO2024188594A1 PCT/EP2024/054118 EP2024054118W WO2024188594A1 WO 2024188594 A1 WO2024188594 A1 WO 2024188594A1 EP 2024054118 W EP2024054118 W EP 2024054118W WO 2024188594 A1 WO2024188594 A1 WO 2024188594A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber composite
coating
rubber
metal
steel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/054118
Other languages
English (en)
Inventor
Degui XIA
Baoxing WANG
Hans Vandeputte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bekaert NV SA
Original Assignee
Bekaert NV SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bekaert NV SA filed Critical Bekaert NV SA
Priority to CN202480015207.8A priority Critical patent/CN120958075A/zh
Publication of WO2024188594A1 publication Critical patent/WO2024188594A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the invention relates to a rubber composite.
  • the invention also relates to a method for making the rubber composite.
  • Steel cord for reinforcing rubber articles is normally composed of at least one steel filament with brass coating.
  • the brass coating is contributing to facilitating the adhesion performance between the steel substate and the rubber compound, and the adhesion is attained by the combination of sulphur from the rubber compound with copper from the brass coating of the steel filament.
  • Adhesion performance is very important for a tire.
  • cobalt based organic salts are added into the rubber compound, such as cobalt naphthenate, cobalt stearates or cobalt boron decanoate complexes.
  • the cobalt based organic salts firstly promote the formation of copper sulphide, and secondly improve the retention of the steel cord to rubber bond in hot and humid conditions by suppressing the oxidation of the coating and thereby overgrowth of the adhesion layer.
  • the primary object of the invention is to provide a rubber composite with improved adhesion performance between the steel cord and rubber compound.
  • a second object of the invention is to provide a rubber article comprising a rubber composite with a longer lifetime.
  • a third object of the invention is to provide a method for making a rubber composite with improved adhesion performance between the steel cord and rubber compound.
  • a rubber composite comprising the rubber compound and at least one steel cord embedded in the rubber compound, the steel cord comprises at least one steel filament, the steel filament has a coating, the coating comprises copper, zinc and a metal M being selected from the group consisting of nickel, tin, indium, manganese, iron, bismuth, cobalt and molybdenum, when the rubber composite is in humid aged condition, with the oxidation reaction of the coating, ZnO layer is present on the remaining unoxidized part of the coating at the contact portion of the steel filament and the rubber compound, and at at least one section (A) in a direction perpendicular to the surface of the steel cord, the ZnO layer has a thickness of at least 50nm and the remaining unoxidized part of the coating has a thickness of at least 50nm, wherein the metal M is present in the ZnO layer of the section (A) with more than 5% expressed as weight percent related to the total of C, 0, S, Cu,
  • the invention provides a rubber composite that has sufficient metallic element M content in ZnO layer even when the ZnO layer has a thickness of more than 50nm, the sufficient metallic element M content can delay the dezincification and the consumption of the coating, the adhesion performance of the steel cord with the rubber compound is improved, thereby the lifetime of the rubber composite or the rubber article comprising the rubber composite is prolonged.
  • every cross-section of the aged rubber composite has at least one section (A) which has a high content of the metal M.
  • the section (A) is one part of the cross-section of the rubber composite in the direction perpendicular to the surface of the steel cord, and it at least includes the area starting from the steel substrate and extending into the rubber compound, and the section (A) includes a part of coating (the unoxidized) and a part of ZnO.
  • the at least one section (A) i.e.
  • the total of the sections (A) covers at least 30% of the circumference length of the steel substrate, for example 30%-70% of the circumference length of the steel substrate. Due to the rough surface of the steel substate or the noncontacting between the surface of the steel filament and the rubber compound in the case of incomplete rubber penetration, it is impossible to have the at least one section (A) covering 100% of the circumference length of the steel substrate for an aged rubber composite.
  • the content of metal M present in the ZnO layer of the section (A) is more than 7% expressed as weight percent related to the total of C, 0, S, Cu, Zn and metal M as determined by line scanning of Energy Dispersive X-ray Spectroscopy. More preferably, metal M present in the ZnO layer of the section (A) accounts for more than 10% and less than 30% expressed as weight percent related to the total of C, O, S, Cu, Zn and metal M as determined by line scanning of Energy Dispersive X-ray Spectroscopy.
  • the metal M is iron preferably.
  • the more presence of iron in the ZnO layer is beneficial for the suppression of dezincification.
  • the copper content inside the coating is within the range from 58 weight percent to 75 weight percent, the content of metal M inside the coating is within the range from 0.5 weight percent to 10 weight percent, the remainder being zinc and unavoidable impurities.
  • the mass of the coating is 2.0-8.0 g/kg for the steel filament prior to the aging of the rubber composite.
  • the steel cord could be any one of existing steel cord construction comprising at least one steel filament, such as monofilament, 1 +n, 2+n, nx1 , nxm, nxmxl, m+n, m+n+l and etc..
  • the invention is developed for reducing the use of cobalt in the rubber compound.
  • the rubber compound of the invention could be cobalt-containing rubber compound or cobalt-free rubber compound.
  • Cobalt-free rubber compound means the rubber compound, as a raw material for making the rubber composite, has no cobalt.
  • the rubber compound could be any one of existing rubber compound for rubber articles such as tire, conveyor belt or hose.
  • a rubber article is provided, the rubber article comprises at least one invention rubber composite.
  • the rubber article comprising the invention rubber composite has a prolonged lifetime.
  • the rubber article could be any one of existing rubber product, such as a tire, a hose or a conveyor belt.
  • the rubber composite is in the belt layer, the carcass layer, the chafer layer and/or the bead of the tire, and the tire could have one or more invention rubber composite.
  • a method for making a rubber composite comprises the following steps: a. providing an intermediate steel wire with a controlled circumferential roughness; b. coating the intermediate steel wire with copper, zinc and a metal M being selected from the group consisting of nickel, tin, indium, manganese, iron, bismuth, cobalt and molybdenum by electroplating, while the current density of electroplating of the metal M is 2 - 4 A/dm 2 ; c. diffusing the copper, zinc and metal M in a diffusion heat treatment; d. drawing the coated intermediate steel wire in wet wire drawing process, with the resulting steel filament having a coating; e.
  • the circumferential roughness Ra of the intermediate steel wire is controlled to be between 0.15 and 0.30 micrometer.
  • the intermediate steel wire normally has a diameter of 0.9-2.5mm.
  • the intermediate steel wire is an intermediate product in the production of steel cord and prepared for the electroplating of the coating.
  • the surface of the intermediate wire has a certain roughness mainly due to the previous drawing processing for diameter reduction from wire rod, for example with a diameter of 5.5mm, to the intermediate steel wire, so that a lot of valleys exist on the surface of the intermediate steel wire.
  • the invention method controls the roughness of the intermediate steel wire, which results in a relatively more smooth surface of the intermediate steel wire for electroplating, and the presence of big and deep valley on the surface of intermediate steel wire is reduced; furthermore, the current density of the electroplating of metal M is set to be 2 - 4 A/dm 2 , which decreases the amount of the metal M in the deep valley on the surface of intermediate steel wire and improves the uniformity of electroplating of M as well, as thus the presence of metal M is more and evenly distributed in the surface layer of the coating after wet wire drawing, which ensures sufficient metal M in the ZnO layer after the aging of rubber composite.
  • the roughness of the intermediate steel wire can be controlled by any of existing technologies, for example adjusting the lubrication conditions during the wire drawing process from wire rod to intermediate steel wire, or reducing the damage from the acid to the surface of the intermediate steel wire in the acid pickling processing which is for removing the oxide prior to electroplating, via the use of weak acid or the use of corrosion inhibitor.
  • the mass of the coating on intermediate steel wire is preferably 2.0-8.0 g/kg in step b.
  • Figure 1 describes a cross-section of the steel cord out of the aged invention rubber composite by Scanning Electron Microscope (SEM).
  • Figure 2 describes section (A) at the cross-section of the steel cord out of the aged invention rubber composite by SEM.
  • Figure 3 describes a line scanning of Energy Dispersive X-ray Spectroscopy of the invention.
  • An intermediate steel wire is provided from a wire rod.
  • the wire rod with a diameter of 5.0-5.5mm, is firstly cleaned by mechanical descaling and I or by chemical pickling in a H2SO4 or HCI solution in order to remove the oxides present on the surface.
  • the wire rod is then rinsed in water and is dried.
  • the dried wire rod is then subjected to a first series of dry drawing operations in order to reduce the diameter until a first diameter.
  • the dry drawn steel wire is subjected to a first intermediate heat treatment, called patenting.
  • Patenting means first austenitizing until a temperature of about 1000 °C followed by a transformation phase from austenite to pearlite at a temperature of about 600 - 650 °C. The steel wire is then ready for further mechanical deformation.
  • the steel wire is further dry drawn from the first diameter until a second diameter in a second number of diameter reduction steps.
  • the lubrication conditions during the dry drawing is adjusted for improving the roughness of the intermediate steel wire.
  • the second diameter typically ranges from 0.9 mm to 2.5 mm.
  • the steel wire is subjected to a second patenting treatment, i.e. , austenitizing again at a temperature of about 1000 °C and thereafter quenching at a temperature of 600 to 650 °C to allow for transformation to pearlite.
  • a second patenting treatment i.e. , austenitizing again at a temperature of about 1000 °C and thereafter quenching at a temperature of 600 to 650 °C to allow for transformation to pearlite.
  • the wire is then subjected to the pickling in acid for removing the oxide prepared for electroplating, and the roughness of the wire is improved with the use of weak acid or the adding of corrosion inhibitor in the acid.
  • the intermediate steel wire is coated with copper, zinc and a metal M being selected from the group consisting of nickel, tin, indium, manganese, iron, bismuth, cobalt and molybdenum by electroplating.
  • the current density of the electroplating of metal M is set to be 2 - 4 A/dm 2
  • the copper, zinc and the metal M can be coated in any order.
  • the copper, zinc and the metal M is coated in the order of Cu, M and then Zn.
  • the mass of the coating is 2.0-8.0 g/kg.
  • the coated intermediate steel wire is subjected to a diffusion heat treatment to diffuse the copper, zinc and metal M.
  • the coated intermediate steel wire is drawn in wet wire drawing, this results in a steel filament having a coating, and the steel filament has a carbon content higher than 0.60 percent by weight, or no less than 0.70 percent by weight, or even higher than 0.80 or 0.90 percent by weight, with a tensile strength (TS) typically above 2800 MPa and adapted for the reinforcement of rubber articles.
  • Steel filament has a final diameter D ranging from 0.05 mm to 0.60 mm, e.g. from 0.10 mm to 0.50 mm.
  • steel filament diameters are 0.10 mm, 0.12 mm, 0.15 mm, 0.175 mm, 0.18 mm, 0.20 mm, 0.22 mm, 0.245 mm, 0.28 mm, 0.30 mm, 0.32 mm, 0.35 mm, 0.38 mm, 0.40 mm. Better that the diameter the steel filament D is in the range of 0.10mm-0.50mm.
  • Rubber compound is provided and embedded with at least one steel cord thereby to form a green rubber composite, and then the green rubber composite is vulcanized to obtain the final rubber composite.
  • the green rubber composite is vulcanized to obtain the final rubber composite.
  • the fresh rubber composite there is only a few and very thin ZnO on the coating.
  • the rubber composite is aged in humid aged condition, the humid aging condition and time are controlled, for example, 93°C&95%RH for 14days, to obtain a desired thickness of ZnO layer and the remaining unoxidized part of the coating for observing the invention feature, i.e. , the thickness of ZnO layer is at least 50nm, and the thickness of remaining unoxidized part of the coating is at least 50nm.
  • Figure 1 illustrates a SEM picture of the cross-section of the steel cord out of the aged invention rubber composite.
  • the steel cord has a construction of 3x0.28, and each steel filament of the steel cord has a coating of Cu-Fe- Zn with a mass of 3.9 g/kg prior to the aging of the rubber composite.
  • Figure 2 illustrates a SEM picture of the section (A) at the cross-section of the steel cord as illustrated in Figure 1 , that the area in the highlighted white box is the section (A).
  • Figure 3 is a graph illustrating the EDS line scanning result of the section (A) of invention rubber composite. The graph includes the scanning lines of C, 0, S, Cu, Zn and Fe.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ropes Or Cables (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne un composite de caoutchouc, le composite de caoutchouc comprenant le composé de caoutchouc et au moins un câble d'acier intégré dans le composé de caoutchouc, le câble d'acier comprenant au moins un filament d'acier, le filament d'acier comportant un revêtement, le revêtement comprenant du cuivre, du zinc et un métal M qui est choisi dans le groupe constitué par le nickel, l'étain, l'indium, le manganèse, le fer, le bismuth, le cobalt et le molybdène, lorsque le composite de caoutchouc est dans un état de vieillissement humide, la réaction d'oxydation dudit revêtement, de la couche de ZnO étant présente sur la partie non oxydée restante du revêtement au niveau de la partie de contact du filament d'acier et du composé de caoutchouc, et au moins une section (A) dans une direction perpendiculaire à la surface du câble d'acier, la couche de ZnO présente une épaisseur d'au moins 50 nm et la partie non oxydée restante dudit revêtement présente une épaisseur d'au moins 50 nm, le métal M étant présent dans la couche de ZnO de la section (A) avec plus de 5 % exprimés en pourcentage en poids associé au total de C, O, S, Cu, Zn et de métal M tel que déterminé par balayage linéaire de spectroscopie de rayons X à dispersion d'énergie. Le composite de caoutchouc de l'invention présente des performances d'adhérence améliorées.
PCT/EP2024/054118 2023-03-14 2024-02-19 Composite de caoutchouc et procédé de fabrication du composite de caoutchouc Pending WO2024188594A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202480015207.8A CN120958075A (zh) 2023-03-14 2024-02-19 橡胶复合材料和用于制备橡胶复合材料的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/CN2023/081410 WO2024187381A1 (fr) 2023-03-14 2023-03-14 Composite de caoutchouc et procédé de fabrication du composite de caoutchouc
CNPCT/CN2023/081410 2023-03-14

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Publication Number Publication Date
WO2024188594A1 true WO2024188594A1 (fr) 2024-09-19

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PCT/EP2024/054118 Pending WO2024188594A1 (fr) 2023-03-14 2024-02-19 Composite de caoutchouc et procédé de fabrication du composite de caoutchouc

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CN (1) CN120958075A (fr)
WO (2) WO2024187381A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4446198A (en) 1983-09-08 1984-05-01 The Goodyear Tire & Rubber Company Copper-zinc-iron ternary alloy coated steel wire reinforcers in tires
US4859289A (en) * 1986-05-26 1989-08-22 Sumitomo Electric Industries, Ltd. Process for producing a metal wire useful as rubber product reinforcement
JPH1193086A (ja) * 1997-09-10 1999-04-06 Ohtsu Tire & Rubber Co Ltd :The タイヤ用スチールコード
WO2013117249A1 (fr) 2012-02-06 2013-08-15 Nv Bekaert Sa Revêtement en alliage ternaire ou quaternaire pour vieillissement à la vapeur et élément allongé en acier à adhérence par durcissement à l'humidité comprenant un revêtement en alliage de laiton ternaire ou quaternaire et procédé correspondant
WO2013117248A1 (fr) 2012-02-06 2013-08-15 Nv Bekaert Sa Elément allongé en acier comprenant un revêtement en alliage de laiton ternaire ou quaternaire et procédé correspondant
CN111497526A (zh) * 2020-04-16 2020-08-07 江苏通用科技股份有限公司 一种载重子午线轮胎胎体结构

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4446198A (en) 1983-09-08 1984-05-01 The Goodyear Tire & Rubber Company Copper-zinc-iron ternary alloy coated steel wire reinforcers in tires
US4859289A (en) * 1986-05-26 1989-08-22 Sumitomo Electric Industries, Ltd. Process for producing a metal wire useful as rubber product reinforcement
JPH1193086A (ja) * 1997-09-10 1999-04-06 Ohtsu Tire & Rubber Co Ltd :The タイヤ用スチールコード
WO2013117249A1 (fr) 2012-02-06 2013-08-15 Nv Bekaert Sa Revêtement en alliage ternaire ou quaternaire pour vieillissement à la vapeur et élément allongé en acier à adhérence par durcissement à l'humidité comprenant un revêtement en alliage de laiton ternaire ou quaternaire et procédé correspondant
WO2013117248A1 (fr) 2012-02-06 2013-08-15 Nv Bekaert Sa Elément allongé en acier comprenant un revêtement en alliage de laiton ternaire ou quaternaire et procédé correspondant
CN111497526A (zh) * 2020-04-16 2020-08-07 江苏通用科技股份有限公司 一种载重子午线轮胎胎体结构

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Publication number Publication date
WO2024187381A1 (fr) 2024-09-19
CN120958075A (zh) 2025-11-14

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