EP3642382B1 - Fil avec âme en acier et avec d'un revêtement d'alliage métallique - Google Patents

Fil avec âme en acier et avec d'un revêtement d'alliage métallique Download PDF

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Publication number
EP3642382B1
EP3642382B1 EP18729895.5A EP18729895A EP3642382B1 EP 3642382 B1 EP3642382 B1 EP 3642382B1 EP 18729895 A EP18729895 A EP 18729895A EP 3642382 B1 EP3642382 B1 EP 3642382B1
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EP
European Patent Office
Prior art keywords
layer
zinc
copper
wire
per cent
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Active
Application number
EP18729895.5A
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German (de)
English (en)
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EP3642382A1 (fr
Inventor
Simone Agresti
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
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Bekaert NV SA
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Publication of EP3642382A1 publication Critical patent/EP3642382A1/fr
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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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • 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
    • B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21F—WORKING OR PROCESSING OF METAL WIRE
    • B21F19/00—Metallic coating of wire
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/60—After-treatment
    • 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
    • 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
    • D07B2201/2001—Wires or filaments
    • D07B2201/201—Wires or filaments characterised by a coating
    • D07B2201/2013—Wires or filaments characterised by a coating comprising multiple layers
    • 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

Definitions

  • the invention relates to a wire having a core of steel and a metal coating and to a method of manufacturing and further processing such a wire.
  • Steel wires with a metal alloy coating e.g. a brass coating
  • the alloy coating is obtained by first plating the separate metals one after the other, followed by a heat treatment to diffuse the metals into an alloy. High demands are made upon these steel wires such as a high tensile strength and a high level of adhesion to rubber.
  • Steel wires with a metal alloy coating are also known for use as loose abrasive sawing wire for the cutting of silicon ingots.
  • the alloy coating is here also obtained by first plating the separate metals one of the other, followed by a heat treatment to diffuse the metals into an alloy. High demands are also made upon these sawing wires such as, particularly, a high tensile strength.
  • the steel wire has two layers of metal coating:
  • Steel wires with a diameter ranging from 0.30 mm to 1.0 mm are suitable intermediate products to make loose abrasive sawing wire.
  • Steel wires with a diameter ranging from 0.90 mm to 3.0 mm are suitable intermediate products to make steel filaments adapted for rubber reinforcement.
  • the heating treatment for diffusion of the two or more metals in the alloy can be less intense. Hence loss of tensile strength can either be avoided or even not be present. So the intermediate steel wires have a higher starting tensile strength. As a result, for equal degrees of deformation, the final tensile strength is higher or for equal final tensile strengths, the degree of deformation can be lower.
  • the second top layer of copper above the first layer improves the deformability, reduces coating losses, reduces die wear and reduces lubricant consumption.
  • Prior art document WO-A1-2011/076746 discloses a brass coated steel wire with a zinc gradient in the coating.
  • the zinc gradient is such that, in contrast to the invention, less zinc is present at the surface of the brass layer.
  • EP-B1-1295 985 discloses a steel wire with two layers of metal coating.
  • the first layer is a brass coating
  • the second top layer is a copper layer.
  • EP-B1-1 295 985 does not teach the presence of a zinc gradient in the first layer.
  • the top layer of copper has a thickness which is smaller than 0.02 ⁇ m
  • US4686153 is related to EDM of electrical wires and discloses creating a steel wire (11) with a copper layer (12) and with an outer CuZn-layer (14).
  • the concentration gradient created by diffusion of the outer layer is such that concentration of zinc increases towards the outside. (See figures 2-6 , abstract, columns 5-7). Hence, there is no pure upper copper layer present.
  • the first layer is a copper-M-zinc alloy, where M is one or more metals selected from the group consisting of cobalt, nickel, tin, indium, manganese, iron, bismuth and molybdenum.
  • M is one or more metals selected from the group consisting of cobalt, nickel, tin, indium, manganese, iron, bismuth and molybdenum.
  • the first layer and the second layer together may have a copper content ranging from 58 wt% to 75 wt%, e.g. from 61 wt% to 70 wt%.
  • the content of the one or two metals M may range from 0.5 wt% to 10 wt%, e.g. from 2 wt% to 8 wt%.
  • the first layer is a copper-zinc alloy, only having copper and zinc as main elements.
  • the first layer and the second layer together may have a copper content ranging from 60 wt% to 70 wt%, e.g. from 61 wt% to 69 wt%.
  • the terms "clearly showing a zinc gradient with zinc being more present at the outer side” preferably refer to a configuration where there is Xout per cent of zinc at the outer side of the first layer and Xin per cent of zinc at the inner side of the first layer and where the difference Xout - Xin is more than 15 percent, e.g. more than 16 per cent, e.g. more than 17 per cent, e.g. more than 18 per cent.
  • the weight percentage of copper over the first and the second layer is more than 58 wt%. In a preferable embodiment of the invention, the weight percentage of copper is lower than 70 wt%.
  • the second layer of copper has preferably a thickness more than 0.10 ⁇ m, e.g. more than 0.12 ⁇ m, e.g. more than 0.15 ⁇ m.
  • a method of manufacturing a steel wire comprises the following steps:
  • the zinc gradient there is Xout per cent of zinc at the outer side of the first layer and Xin per cent of zinc at the inner side of the first layer and where the difference Xout - Xin is more than 15 percent, e.g. more than 16 per cent, e.g. more than 17 per cent, e.g. more than 18 per cent.
  • the method further comprises the step of drawing the steel wire so that the copper of the second layer and the two or more metals of the first layer diffuse into each other and form one global layer.
  • the diffusion as a result of the drawing operation is such that the outer side of the global layer has Xgout per cent of zinc and the inner side of the global layer has Xgin per cent of zinc, where Xgout - Xgin is less than 15 per cent, e.g. less than 14 per cent, e.g. less than 12 per cent.
  • FIG. 1 illustrates in a schematic way a prior art process.
  • a steel wire 10 is first plated with copper (Cu) in a copper plating installation 12 in an amount equal to the final amount of copper needed or desired.
  • the copper plated wire is then coated with zinc (Zn) in a zinc plating installation 14 in an amount equal to the final amount of zinc needed or desired.
  • the steel wire with the double coating is then subjected to a thermodiffusion treatment, e.g. by means of a mid-frequent installation 16.
  • the thickness of the brass coating is represented in 17.
  • the amount of thermodiffusion energy spent is such that a full alloying of copper with zinc is obtained, or at least approximated. This means that a gradient of zinc throughout this brass coating is non-existent or limited to maximum 15%, preferably maximum 10%.
  • the result of this prior art process is a steel wire 18 with a more or less homogeneous brass coating.
  • FIG. 2 illustrates the present invention.
  • a steel wire 20 enters into a copper plating bath 22 where only 75% to 85% of the amount of finally desired or needed copper is deposited on the steel 20. Thereafter the steel wire enters into a zinc plating installation 24 where 100% of the amount of the finally desired or needed zinc is deposited.
  • the steel wire with the double layer is then subjected to a thermodiffusion treatment in, e.g. a mid-frequent installation 26.
  • a thermodiffusion treatment in, e.g. a mid-frequent installation 26.
  • only a partial alloying is aimed at, which means that only a partial diffusion is carried out thus saving 15 to 30% of thermodiffusion energy.
  • the thickness of the partially alloyed copper-zinc coating is illustrated in 27.
  • the steel wire is plated with the remaining 25% to 15% of copper in a second copper plating installation 28.
  • an intermediate wire 30 with a first layer of a copper-zinc alloy that is showing a clear gradient of zinc with zinc being more present at the outer side and a second layer of copper on top and around of the first layer. Due to its top copper coating, this intermediate wire 30 has a color that is more red than a wire with a common brass coating.
  • the partial diffusion treatment in the installation 26 bounds the zinc to copper, despite the presence of a zinc gradient. This bounding prevents the zinc from dissolving in the second copper bath 28.
  • thermodiffusion treatment has as additional advantage that the loss in tensile strength of the intermediate steel wire is either non-existent or substantially reduced. All other parameters being unchanged, this means that the tensile strength before the beginning of the wet wire drawing operation is higher than it is in the prior art. Tests have shown differences in tensile strength between the prior art and the invention that vary between 10 MPa and 25 MPa.
  • a cross-section of the double coated intermediate steel wire 30 is shown in Figure 3 .
  • the steel wire 30 has a steel core 32, a first layer of a partially alloyed copper-zinc coating 34 and a second layer of copper 36 on top of the first layer 34.
  • Figure 4 shows a cross-section of a final steel filament 40. It has a steel core 42 and a single 'global' layer of brass 44 without gradient or with a gradient that is less pronounced than the gradient of the intermediate steel wire 30.
  • wet wire drawing is the process that transforms the intermediate steel wire 30 into the final steel filament 40.
  • the heat generated during the wet wire drawing process causes the first layer and the second to diffuse with each other in order to result in a brass coating that is more or less homogeneous.
  • top copper coating 36 that causes less slip than a brass or a zinc coating.
  • the further downstream processing such as the cord twisting also has its advantages when handling a steel filament that originates from an intermediate steel wire according to the invention. More particularly, a substantial reduction in the number of fractures has been noticed. For one particular steel cord construction made by a double-twisting ("bunching") process, the level of fractures per ton was reduced with 50%.
  • the single brass coating has a zinc gradient that is much smaller than that of the first layer of an intermediate steel wire 30.
  • 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%, even of 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% ranging from 0.05% to 0.50%
  • a maximum sulphur content of 0.03% ranging from 0.05% to 0.50%
  • a maximum sulphur content of 0.03% a maximum phosphorus content of 0.03%
  • even of 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:
  • low-carbon steel compositions such as disclosed in EP-A-2 268 839 are not excluded.
  • Such a steel compositions 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Ropes Or Cables (AREA)
  • Metal Extraction Processes (AREA)

Claims (11)

  1. Fil
    possédant un noyau d'acier doté d'un diamètre dans la plage de 0,30 mm à 3,0 mm, ledit fil possédant deux couches de revêtement métallique :
    - une première couche d'un alliage de zinc autour dudit noyau et présentant clairement un gradient de zinc, le zinc étant plus présent au niveau du côté externe,
    - une deuxième couche de cuivre autour de ladite première couche.
  2. Fil selon la revendication 1,
    ladite première couche étant un alliage cuivre-M-zinc, dans lequel M est un ou deux métaux choisis dans le groupe constitué par le cobalt, le nickel, l'étain, l'indium, le manganèse, le fer, le bismuth et le molybdène.
  3. Fil selon la revendication 1,
    ladite première couche étant un alliage cuivre-zinc.
  4. Fil selon l'une quelconque des revendications précédentes,
    ledit côté externe de ladite première couche possédant Xext pour cent de zinc et ledit côté interne de ladite première couche possédant Xint pour cent de zinc, Xext - Xint étant supérieur à 15 pour cent.
  5. Fil selon l'une quelconque des revendications 2 à 4,
    le pourcentage en poids de cuivre dans à la fois la première et la deuxième couche étant supérieur à 58 % en poids.
  6. Fil selon la revendication 5,
    le pourcentage en poids de cuivre dans la première et la deuxième couche étant inférieur à 70 % en poids.
  7. Fil selon l'une quelconque des revendications précédentes,
    la deuxième couche possédant une épaisseur supérieure à 0,10 µm.
  8. Procédé de fabrication d'un fil, ledit procédé comprenant les étapes suivantes :
    a. mise à disposition d'un noyau d'acier doté d'un diamètre dans la plage entre 0,30 mm et 3,0 mm ;
    b. placage dudit noyau d'acier avec deux métaux ou plus, l'un d'eux étant le zinc ;
    c. chauffage du noyau d'acier ainsi plaqué de sorte que les deux métaux ou plus diffusent partiellement et forment une première couche, présentant clairement un gradient de zinc, le zinc étant plus présent au niveau du côté externe que du côté interne ;
    d. placage d'une deuxième couche de cuivre autour de ladite première couche.
  9. Procédé selon la revendication 8,
    ledit côté externe de ladite première couche possédant Xext pour cent de zinc et ledit côté interne de ladite première couche possédant Xint pour cent de zinc, Xext - Xint étant supérieur à 15 pour cent.
  10. Procédé selon la revendication 8 ou 9,
    ledit procédé comprenant en outre l'étape de :
    e. tirage dudit fil d'acier de sorte que le cuivre de la deuxième couche et les deux métaux ou plus de la première couche diffusent l'un dans l'autre et forment une couche globale.
  11. Procédé selon la revendication 10,
    la diffusion résultant dudit tirage étant telle que ledit côté externe de ladite couche globale possède Xgext pour cent de zinc et ledit côté interne de ladite couche globale possède Xgint pour cent de zinc, Xgext - Xgint étant inférieur à 15 pour cent.
EP18729895.5A 2017-06-22 2018-05-28 Fil avec âme en acier et avec d'un revêtement d'alliage métallique Active EP3642382B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17177407 2017-06-22
PCT/EP2018/063955 WO2018233986A1 (fr) 2017-06-22 2018-05-28 Fil avec âme en acier et revêtement d'alliage métallique

Publications (2)

Publication Number Publication Date
EP3642382A1 EP3642382A1 (fr) 2020-04-29
EP3642382B1 true EP3642382B1 (fr) 2021-03-31

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP18729895.5A Active EP3642382B1 (fr) 2017-06-22 2018-05-28 Fil avec âme en acier et avec d'un revêtement d'alliage métallique

Country Status (5)

Country Link
EP (1) EP3642382B1 (fr)
CN (1) CN110785510B (fr)
ES (1) ES2860579T3 (fr)
HU (1) HUE053878T2 (fr)
WO (1) WO2018233986A1 (fr)

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JP7296388B2 (ja) * 2018-08-07 2023-06-22 住友電気工業株式会社 銅被覆鋼線および撚線
PT3702638T (pt) * 2019-02-26 2021-08-12 Bekaert Sa Nv Atuador para abrir e fechar uma porta ou uma bagageira de um carro

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US4686153A (en) * 1984-12-08 1987-08-11 Fujikura Ltd. Electrode wire for use in electric discharge machining and process for preparing same
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JPS61284321A (ja) * 1985-06-06 1986-12-15 Fujikura Ltd ワイヤ放電加工用電極線
JPS61284322A (ja) * 1985-06-06 1986-12-15 Fujikura Ltd ワイヤ放電加工用電極線
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BRPI0908575A2 (pt) 2008-03-04 2015-09-22 Bekaert Sa Nv filamento de aço com baixo teor de carbono trefilado a frio e método de fabricação do referido filamento
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Also Published As

Publication number Publication date
HUE053878T2 (hu) 2021-07-28
CN110785510A (zh) 2020-02-11
WO2018233986A1 (fr) 2018-12-27
CN110785510B (zh) 2021-12-31
ES2860579T3 (es) 2021-10-05
EP3642382A1 (fr) 2020-04-29

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