US20140378597A1 - Elongated steel element comprising a ternary or quaternary brass alloy coating and corresponding method - Google Patents

Elongated steel element comprising a ternary or quaternary brass alloy coating and corresponding method Download PDF

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Publication number
US20140378597A1
US20140378597A1 US14/375,295 US201214375295A US2014378597A1 US 20140378597 A1 US20140378597 A1 US 20140378597A1 US 201214375295 A US201214375295 A US 201214375295A US 2014378597 A1 US2014378597 A1 US 2014378597A1
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coating
weight percent
elongated steel
steel element
copper
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Guy Buytaert
Dieter Wemel
Patricia Reis
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Bekaert NV SA
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Bekaert NV SA
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Assigned to NV BEKAERT SA reassignment NV BEKAERT SA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WEMEL, Dieter, REIS, Patricia, BUYTAERT, GUY
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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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/02—Drawing metal wire or like flexible metallic material by drawing machines or apparatus in which the drawing action is effected by drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • 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
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/12—Threads containing metallic filaments or strips
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • 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
    • B60C2009/0014—Surface treatments of steel cords
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • 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
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    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/066—Reinforcing cords for rubber or plastic articles the wires being made from special alloy or special steel composition
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2001—Wires or filaments
    • D07B2201/201—Wires or filaments characterised by a coating
    • D07B2201/2011—Wires or filaments characterised by a coating comprising metals
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2015—Strands
    • D07B2201/2042—Strands characterised by a coating
    • D07B2201/2043—Strands characterised by a coating comprising metals
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/30—Inorganic materials
    • D07B2205/3021—Metals
    • D07B2205/3085—Alloys, i.e. non ferrous
    • D07B2205/3089—Brass, i.e. copper (Cu) and zinc (Zn) alloys
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2501/00—Application field
    • D07B2501/20—Application field related to ropes or cables
    • D07B2501/2046—Tire cords

Definitions

  • the present invention relates to an elongated steel element adapted for the reinforcement of rubber products.
  • the present invention also relates to a process for manufacturing such an elongated steel element.
  • Elongated steel elements such as brass coated steel wires and steel cords are widely used to reinforce rubber products such as tires.
  • cobalt complexes are added to the rubber compound.
  • cobalt is considered to be a poison for the rubber since, like most transition metals, it is an oxidation catalyst.
  • oxidation of diene rubber molecules will be accelerated due to the presence of cobalt, which leads to earlier rubber ageing.
  • cobalt also speeds up crack growth rate of the rubber.
  • Cobalt is a strategic material and it is quite expensive. By adding cobalt to the whole rubber compound, one adds too much cobalt since it has only a positive function at the brass surface. Generally, it is considered that only 20% of the cobalt added to the rubber is used effectively.
  • GB-A-2 076 320 (Soracetal) teaches a thin layer of cobalt on top of a brass coating followed by a wire drawing so that there is a high gradient of cobalt on top of the brass coating.
  • EP-A1-0 175 632 (Goodyear) teaches a quaternary alloy coating copper-zinc-nickel-cobalt on steel elements.
  • WO-A1-2011/076746 discloses a steel cord with a ternary or quaternary alloy coating and with a zinc gradient. Although giving improvement with respect to adhesion, this zinc gradient involves a post-treatment of the wire or cord, meaning an extra operation step in the process.
  • an elongated steel element adapted for the reinforcement of rubber products.
  • This elongated steel element is covered with a ternary alloy or quaternary alloy of a copper-M-zinc coating.
  • M is one or two metals selected from the group consisting of cobalt, nickel, tin, indium, manganese, iron, bismuth and molybdenum.
  • the copper content inside this coating ranges from 58 weight percent to 75 weight percent, e.g. from 61 wt % to 70 wt %.
  • the content of the one or two metals inside the coating ranges from 0.5 weight percent to 10 weight percent, e.g. 2 wt % to 8 wt %.
  • the one or two metals are present throughout the coating, and not only present at the immediate surface.
  • the remainder is zinc and unavoidable impurities, e.g. impurities in quantities lower than 0.1 wt %.
  • the thickness of the coating ranges from 0.05 ⁇ m to 0.50 ⁇ m, e.g. from 0.12 ⁇ m to 0.40 ⁇ m.
  • the weight percentages of copper, the one or two metals and the balance of zinc may be measured by an analytical dissolution technique and with X-ray fluorescence (XRFS), Inductively Coupled Plasma (ICP), Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) or Atomic Absorption Spectroscopy (AAS). These measurements are also suitable to obtain the coating weight and the coating thickness.
  • XRFS X-ray fluorescence
  • ICP Inductively Coupled Plasma
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry
  • AAS Atomic Absorption Spectroscopy
  • Phosphorus is present on or in the coating in an amount ranging from 0.3 milligram per square meter to 1 milligram per square meter of the coating, e.g less than 0.99 mg/m 2 , e.g. less than 0.95 mg/m 2 . Examples of under limits are 0.4 mg/m 2 and 0.5 mg/m 2 .
  • This phosphorus amount may be present in the form of phosphates. The phosphorus amount may be measured by means of an Inductively Coupled Plasma technique or by an ultraviolet-visible spectroscopy.
  • the coating or the surface of the coating is further lacking residues of compounds that complex with the copper in the coating to form an insoluble film.
  • These compounds include triazoles, imidazoles and indazoles.
  • Such compounds include those having the following structural formula:
  • a and B are selected from a group consisting of —N- or —CH-, with A and B never being simultaneously equal to —CH-.
  • examples of such compounds are benzotriazole, tolyltriazole, benzimidazole, indazole, naphthatriazole.
  • the absence of these residues may be measured by a Time of Flight—Secondary Ion Mass Spectrometry (ToF-SIMS) technique.
  • This technique provides information on the atomic and molecular composition of the uppermost 1-3 monolayers with sensitivities at ppm level and lateral resolutions down to 100 nm.
  • ToF-SIMS is not an inherently quantitative technique because the detected intensities depend on the chemical composition of the ambient material (“matrix effect”). Semi-quantitative information can be obtained if the chemical environment of the samples to be compared is similar. In spectrometry mode a total mass spectrum of a surface region of interest is acquired. These spectra are usually recorded with high mass resolution and a low number of used primary ions. The high mass resolution is necessary for a reliable identification of secondary ion signals and corresponding sum formulas. The limited number of primary ions guarantees that the detected signals are representative for the original chemical composition of the sample surface (Static SIMS limit). For the ToF-SIMS measurements of the present invention, an ION-TOF “TOF-SIMS IV” SIMS instrument was used. Ion bombardment of the surface was performed using bismuth ions at 25 keV in a bunched mode. Analysis current is 0.2 pA and the analysed area is 100 ⁇ 100 ⁇ m 2 .
  • the elongated steel element may be a steel wire or a steel cord.
  • the invention is not limited to a particular type of construction.
  • adapted for the reinforcement of rubber products refer to steel wires and steel cords with a suitable wire or filament diameter, a suitable steel composition and a suitable tensile strength.
  • a suitable steel composition is e.g. a minimum carbon content of 0.65%, a manganese content ranging from 0.10% to 0.70%, a silicon content ranging from 0.05% to 0.50%, a maximum sulphur content of 0.03%, a maximum phosphorus content of 0.03% and even 0.02%, all percentages being percentages by weight.
  • a minimum carbon content of 0.65% e.g. 0.65%
  • a manganese content ranging from 0.10% to 0.70%
  • a silicon content ranging from 0.05% to 0.50%
  • a maximum sulphur content of 0.03% e.g. a maximum sulphur content of 0.03%
  • a maximum phosphorus content 0.03% and even 0.02%
  • Micro-alloyed steel compositions may also be suitable such as compositions further comprising one or more of following elements:
  • low-carbon steel compositions such as disclosed in EP-A-2 268 839 are not excluded.
  • Such a steel composition has a carbon content of less than 0.20%.
  • An example is a carbon content ranging between 0.04% and 0.08%, a silicon content of 0.166%, a chromium content of 0.042%, a copper content of 0.173%, a manganese content of 0.382%, a molybdenum content of 0.013%, a nitrogen content of 0.006%, a nickel content of 0.077%, a phosphorus content of 0.007%, a sulphur content of 0.013%, all percentages being percentages by weight.
  • the diameter of individual steel wires or steel filaments of elongated steel elements adapted for reinforcement of rubber products usually ranges from 0.03 mm to 1.20 mm, e.g. from 0.10 mm to 0.80 mm, e.g. from 0.15 mm to 0.60 mm.
  • the levels of roughness R a measured on the individual steel wires vary from 0.10 ⁇ m to 2.0 ⁇ m, e.g. from 0.10 ⁇ m to 1.0 ⁇ m, e.g. from 0.10 ⁇ m to 0.30 ⁇ m.
  • the tensile strength of elongated steel elements adapted for the reinforcement of rubber products largely depends upon the diameter and usually ranges from 1500 MPa to 4500 MPa, e.g. from 2000 MPa to 4000 MPa.
  • EP-A1-0 257 667 discloses a brass alloy coating for steel elements for rubber reinforcement, where the brass alloy coating contains small amounts of phosphorus.
  • the phosphorus is described as improving the adhesion between the rubber and the brass.
  • the amount of phosphorus is higher than in the present invention.
  • the process also lacks other steps of treating the elongated steel element with such compounds.
  • the lubricant may be an emulsion or a dispersion.
  • the thus drawn elongated steel elements may be twisted by means of a double-twister, or by means of a tubular twisting machine.
  • the relatively small amounts of phosphorus lead to an improved adhesion behaviour in under cure. Since the phosphorus is added to the ternary alloy or quaternary alloy coating by means of the wet wire drawing lubricant, no additional process step is required to achieve this improved adhesion.
  • the invention also relates to a rubber product reinforced with an elongated steel element with the features as disclosed hereabove.
  • Two sample steel wires with a diameter of 1.98 mm are provided with a ternary alloy coating as follows:
  • Steel wire 1 has following coating composition: 63.5 wt % Cu, 4.0 wt % Co, the remainder being Zn.
  • Steel wire 2 has following coating composition: 67.0 wt % Cu, 4.0 wt % Co, the remainder being Zn.
  • the steel wires are subjected to a final reduction in diameter during a wet wire drawing operation.
  • Lubricant I is the lubricant to be used in the context of the present invention.
  • Lubricant I is an aqueous emulsion containing more than 90% water, an oil, surfactant, soap, phosphorus compound and a pH buffering system. The pH is also partially buffered by working of amines. More particularly, lubricant I comprises phosphates, sulphates, nitrates, O-containing hydrocarbons and fatty acid residues, N-containing hydrocarbons. The phosphates may be present as PO 2 - or as PO 3 - ions.
  • Reference lubricant X is an aqueous emulsion containing more than 90% water, mineral oil, surfactant, soap, phosphorus compound, extreme pressure additive, corrosion inhibitor of the triazole type, e.g. benzotriazole, and a pH buffering system. The pH is also partially buffered by working of amines.
  • lubricant X contains phosphates, CN/CNO, benzotriazole, hydrocarbons, fatty acids and octylphosphate acid.
  • Reference lubricant Y is an aqueous emulsion containing more than 90% water, vegetable oil, surfactant, soap, phosphorus compound, extreme pressure additive, corrosion inhibitor of the triazole type, e.g. benzotriazole, and a pH buffering system. The pH is also partially buffered by working of amines.
  • lubricant Y contains phosphates, CN/CNO, benzotriazole, hydrocarbons, fatty acids and octylphosphate acid.
  • Final steel wire diameter is 0.30 mm. After wet wire drawing the steel wires have been twisted into a 2 ⁇ 0.30 steel cord construction.
  • Table 1 lists, amongst others, the amount of phosphorus on the surface of the ternary alloy coating.
  • Table 2 mentions the results of the pull-out test and of the appearance ratio test in under cure.
  • the invention samples 1-I inv and 2-I-inv clearly perform better both in the pull-out test as in the appearance ratio test.
  • RC is the TC90 time plus 5 minutes and TC90 is the time when the rubber reaches 90% of its maximum torque on a rheometer curve taken at vulcanisation temperature.
  • SA is steam cooking RC samples at 120 ° C. for 1 or 2 days.
  • 3-X-ref was drawn in lubricant X and has 64.30 wt % Cu in its coating and 1.09 mg/m 2 phosphorus on or in its coating.
  • 3-Y-ref was drawn in lubricant Y and has 64.20 wt % Cu in its coating and 1.28 mg/m 2 phosphorus on or in its coating.
  • Table 4 hereunder summarizes the results of a ToF-SIMS analysis carried on steel cord sample 1-I-inv of the invention.
  • the elongated steel elements lack triazoles on the coating, so they also lack benzotriazoles.
  • Table 4 mentions some values for triazoles. However, these values are to be considered as “noise level”. Values higher than 5, e.g. higher than 10 are to be considered as above noise level.
  • Table 5 hereunder mentions two possible tire rubber compound formulations together with its properties where an effective improvement on UC adhesion has been noticed.
  • Tc2 (min) 1.8 3.5 Tc90 (min) 12.0 13.0 M H (dNm) 31.5 30.6 Mooney at 100° C.
  • Viscosity (MU) 66 70 Shore A Hardness 70 66 Breaking load (N) 336 337

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US10619271B2 (en) 2012-02-06 2020-04-14 Nv Bekaert Sa Process for manufacturing an elongated steel element to reinforce rubber products
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US10619271B2 (en) 2020-04-14
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EP2812480A1 (en) 2014-12-17
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