WO2013117248A1 - 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
WO2013117248A1
WO2013117248A1 PCT/EP2012/064475 EP2012064475W WO2013117248A1 WO 2013117248 A1 WO2013117248 A1 WO 2013117248A1 EP 2012064475 W EP2012064475 W EP 2012064475W WO 2013117248 A1 WO2013117248 A1 WO 2013117248A1
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WIPO (PCT)
Prior art keywords
coating
weight per
per cent
elongated steel
steel element
Prior art date
Application number
PCT/EP2012/064475
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English (en)
French (fr)
Inventor
Guy Buytaert
Dieter WEMEL
Patricia REIS
Original Assignee
Nv Bekaert 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 Nv Bekaert Sa filed Critical Nv Bekaert Sa
Priority to KR1020147021689A priority Critical patent/KR101928130B1/ko
Priority to EP12737831.3A priority patent/EP2812480B1/en
Priority to US14/375,295 priority patent/US20140378597A1/en
Priority to JP2014555095A priority patent/JP6069364B2/ja
Priority to BR112014017588-8A priority patent/BR112014017588B1/pt
Priority to CN201280067804.2A priority patent/CN104066882B/zh
Priority to PL12737831T priority patent/PL2812480T3/pl
Priority to RS20171203A priority patent/RS56637B1/sr
Priority to ES12737831.3T priority patent/ES2642918T3/es
Publication of WO2013117248A1 publication Critical patent/WO2013117248A1/en
Priority to US15/952,636 priority patent/US10619271B2/en

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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • 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
    • 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 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
  • 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 (Sodetal) 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 -201 1/076746 discloses a steel cord with a ternary or
  • 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 per cent to 75 weight per cent, e.g. from 61 wt % to 70 wt %.
  • the content of the one or two metals inside the coating ranges from 0.5 weight per cent to 10 weight per cent, 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 ⁇ to 0.50 ⁇ , e.g. from 0.12 ⁇ to 0.40 ⁇ .
  • 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.
  • ToF-SIMS Secondary Ion Mass Spectrometry
  • 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.
  • 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).
  • the elongated steel element may be a steel wire or a steel cord.
  • the invention is not limited to a particular type of
  • the terms "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.
  • Micro-alloyed steel compositions may also be suitable such as
  • compositions further comprising one or more of following elements:
  • - chromium (%Cr) in amounts ranging from 0.10% to 1.0%, e.g. from 0.10 to 0.50%;
  • - nickel (%Ni) in amounts ranging from 0.05% to 2.0%, e.g. from 0.10% to 0.60%;
  • - cobalt (%Co) in amounts ranging from 0.05% to 3.0%; e.g. from 0.10% to 0.60%;
  • - vanadium (%V) in amounts ranging from 0.05% to 1.0%, e.g. from 0.05% to 0.30%;
  • - copper (%Cu) in amounts ranging from 0.10% to 0.40%, e.g. from 0.15% to 0.30%;
  • %B - boron
  • - niobium (%Nb) in amounts ranging from 0.001 % to 0.50%, e.g. from 0.02% to 0.05%;
  • - titanium (%Ti) in amounts ranging from 0.001 % to 0.50%, e.g. from 0.001 % to 0.010%;
  • - antimony (%Sb) in amounts ranging from 0.0005% to 0.08%, e.g. from 0.0005% to 0.05%;
  • - calcium (%Ca) in amounts ranging from 0.001 % to 0.05%, e.g. from 0.0001 % to 0.01 %;
  • %Zr - zirconium
  • - aluminum (%AI) preferably in amounts lower than 0.035%, e.g. lower than 0.015%, e.g. lower than 0.005%;
  • %REM - rare earth metals
  • 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 ⁇ to 2.0 ⁇ , e.g. from 0.10 ⁇ to 1.0 ⁇ , e.g. from 0.10 ⁇ to 0.30 ⁇ .
  • 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.
  • M being one or two metals selected from the group consisting of cobalt, nickel, tin, indium, manganese, iron, bismuth and molybdenum, the copper content inside the coating ranges from 58 weight per cent to 75 weight per cent, the content of the one or two metals inside the coating ranges from 0.5 weight per cent to 10 weight per cent, the remainder is zinc and unavoidable impurities, the one or two metals being present throughout said coating;
  • aqueous lubricant containing a phosphorus compound
  • the amount of phosphorus compound being such that phosphorus is present on the coating in an amount of less than 1 milligram per square meter of the coating.
  • the phosphorus amount is measured by means of an Inductively Coupled Plasma technique.
  • the lubricant further lacks compounds that complex with the copper in the coating to form an isoluble film.
  • 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.
  • 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. [0032] 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
  • 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.
  • lubricant I comprises phosphates, sulphates, nitrates, O- containing hydrocarbons and fatty acid residues, N-containing
  • the phosphates may be present as PO2 ⁇ or as PO3 " 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 2x0.30 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.
  • invention samples 1 -1 inv and 2-l-inv clearly perform better both in the pull-out test as in the appearance ratio test.
  • adhesion behaviour of invention samples 1 -l-inv and 2-l-inv at regular cure (RC) and after steam aging (SA) are at an acceptable high level, see Table 3 hereafter.
  • 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-l-ref was drawn in lubricant I and has 63.95 wt% Cu in its coating and 0.81 mg/m 2 phosphorus on or in its coating.
  • 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 -l-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.
  • Natural rubber TSR10 100 parts 100 parts ZnO - Zinc oxide 9 phr 9 phr
  • the Tan ⁇ at 60°C is an indication of the rolling resistance, the higher the value, the higher the rolling resistance.

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KR1020147021689A KR101928130B1 (ko) 2012-02-06 2012-07-24 삼원계 또는 사원계 황동 합금 코팅을 포함하는 연신된 스틸 요소 및 상응하는 방법
EP12737831.3A EP2812480B1 (en) 2012-02-06 2012-07-24 Elongated steel element comprising a ternary or quaternary brass alloy coating and corresponding method
US14/375,295 US20140378597A1 (en) 2012-02-06 2012-07-24 Elongated steel element comprising a ternary or quaternary brass alloy coating and corresponding method
JP2014555095A JP6069364B2 (ja) 2012-02-06 2012-07-24 三元または四元黄銅合金被覆物を備えた細長い鋼製エレメントおよび対応する方法
BR112014017588-8A BR112014017588B1 (pt) 2012-02-06 2012-07-24 Elemento de aço alongado adaptado para reforço de produtos de borracha, processo para produzir um elemento de aço alongado adaptado para reforço de produtos de borracha e artigo de borracha reforçado
CN201280067804.2A CN104066882B (zh) 2012-02-06 2012-07-24 包含三元或四元黄铜合金涂层的狭长钢元件及相应的方法
PL12737831T PL2812480T3 (pl) 2012-02-06 2012-07-24 Podłużny element stalowy zawierający powłokę z trójskładnikowego lub czteroskładnikowego stopu mosiężnego i odpowiedni sposób
RS20171203A RS56637B1 (sr) 2012-02-06 2012-07-24 Izduženi čelični element koji sadrži sloj od ternarne ili kvaternarne legure od mesinga i odgovarajući postupak
ES12737831.3T ES2642918T3 (es) 2012-02-06 2012-07-24 Elemento de acero alargado que comprende un recubrimiento de aleación de latón ternaria o cuaternaria y método correspondiente
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US20170021670A1 (en) * 2014-04-11 2017-01-26 Bridgestone Corporation Resin-metal composite material and tire using same
WO2020156967A1 (en) 2019-01-31 2020-08-06 Nv Bekaert Sa Steel cord with a brass coating enriched with iron particles
WO2021249922A1 (en) 2020-06-11 2021-12-16 Nv Bekaert Sa Brass coated steel cord with increased iron content at the surface

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SI2812481T1 (sl) 2012-02-06 2019-01-31 Nv Bekaert Sa Podolgovat jeklen element, ki vsebuje oplaščenje iz ternarne ali kvaternarne medeninaste zlitine in odgovarjajoči postopek
WO2013117248A1 (en) 2012-02-06 2013-08-15 Nv Bekaert Sa Elongated steel element comprising a ternary or quaternary brass alloy coating and corresponding method
JP6537966B2 (ja) * 2012-07-24 2019-07-03 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニムＮ Ｖ Ｂｅｋａｅｒｔ Ｓｏｃｉｅｔｅ Ａｎｏｎｙｍｅ 選択的に真鍮が被覆されたフィラメントを有するゴム補強用鋼コード
JP6316286B2 (ja) * 2013-05-30 2018-04-25 株式会社ブリヂストン 金属コード−ゴム複合体の製造方法
CN106011531A (zh) * 2016-06-29 2016-10-12 南通恒金复合材料有限公司 一种改进的汽车水箱散热器用铜带
WO2019159531A1 (ja) 2018-02-14 2019-08-22 住友電気工業株式会社 タイヤ
KR102125998B1 (ko) 2018-03-12 2020-07-02 홍덕산업(주) 내산화성이 우수한 전기 도금 비드와이어
RU2768910C1 (ru) * 2019-04-25 2022-03-25 Трефил Арбед Корея Ко., Лтд. Стальной корд для улучшения резины и способ его производства
EP3882374A1 (de) * 2020-03-18 2021-09-22 voestalpine Stahl GmbH Verfahren zur erzeugung von bereichen mit unterschiedlichen optischen eigen-schaften auf verzinkten stahlbändern und verzinkte stahlbänder mit bereichen mit unterschiedlichen optischen eigenschaften
JPWO2023276641A1 (US20100136652A1-20100603-C00017.png) * 2021-06-30 2023-01-05
JP2023173220A (ja) 2022-05-25 2023-12-07 住友ゴム工業株式会社 タイヤ

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US20170021670A1 (en) * 2014-04-11 2017-01-26 Bridgestone Corporation Resin-metal composite material and tire using same
JP2016044370A (ja) * 2014-08-22 2016-04-04 新日鐵住金株式会社 ゴムとの接着性に優れた極細めっき鋼線およびそれを用いたゴム複合体
WO2020156967A1 (en) 2019-01-31 2020-08-06 Nv Bekaert Sa Steel cord with a brass coating enriched with iron particles
US11905654B2 (en) 2019-01-31 2024-02-20 Nv Bekaert Sa Steel cord with a brass coating enriched with iron particles
WO2021249922A1 (en) 2020-06-11 2021-12-16 Nv Bekaert Sa Brass coated steel cord with increased iron content at the surface

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RS56637B1 (sr) 2018-03-30
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ES2642918T3 (es) 2017-11-20
US10619271B2 (en) 2020-04-14
PL2812480T3 (pl) 2018-02-28
PT2812480T (pt) 2017-10-18
EP2812480A1 (en) 2014-12-17
BR112014017588A2 (US20100136652A1-20100603-C00017.png) 2017-06-20
KR101928130B1 (ko) 2018-12-11
JP2015511998A (ja) 2015-04-23

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