EP1004689B1 - Beschichtete Metalldrähte und Herstellungsverfahren - Google Patents

Beschichtete Metalldrähte und Herstellungsverfahren Download PDF

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Publication number
EP1004689B1
EP1004689B1 EP99121011.3A EP99121011A EP1004689B1 EP 1004689 B1 EP1004689 B1 EP 1004689B1 EP 99121011 A EP99121011 A EP 99121011A EP 1004689 B1 EP1004689 B1 EP 1004689B1
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EP
European Patent Office
Prior art keywords
copper
wire
metal wire
zinc
layers
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.)
Expired - Lifetime
Application number
EP99121011.3A
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English (en)
French (fr)
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EP1004689A2 (de
EP1004689A3 (de
Inventor
Siegfried Doujak
Federico Pavan
Andrea Pieralli
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Pirelli Tyre SpA
Original Assignee
Pirelli SpA
Pirelli Tyre SpA
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Publication date
Application filed by Pirelli SpA, Pirelli Tyre SpA filed Critical Pirelli SpA
Priority to EP99121011.3A priority Critical patent/EP1004689B1/de
Publication of EP1004689A2 publication Critical patent/EP1004689A2/de
Publication of EP1004689A3 publication Critical patent/EP1004689A3/de
Application granted granted Critical
Publication of EP1004689B1 publication Critical patent/EP1004689B1/de
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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
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires

Definitions

  • the invention relates to metal wire particularly adapted for drawing to form a brass surface coating thereon, a resulting brass-coated metal wire adapted for use in wire reinforced elastomeric articles, such as vehicle tires, hoses, conveyor belts, a wire-reinforced elastomeric article containing this wire, and a method for producing the brass coated metal wire.
  • metal wires as reinforcement components of the article.
  • this reinforcement is achieved by embedding coated metallic wires in the elastomeric compound material of the tire, especially when the elastomeric compound material is used in the belts and carcass of the tire.
  • the wires have a coating to improve the adhesion of the wire to the elastomeric compound material of the tire, and to inhibit corrosion of the metal wire.
  • the metal wire can corrode if it enters in contact with the atmosphere, for example due to damage to the elastomeric compound material, and the corrosion can spread along the wire to other portions of the tire.
  • This prior-art practice has the disadvantage of requiring an excessive number of manufacturing steps. For example, it is necessary after the plurality of deposition steps and the diffusion step to pickle the resulting brass coating in an acid solution to remove the zinc oxide formed at the relatively high temperatures and long times necessary to achieve the required diffusion, and to insure a slight phosphorization of the wire which facilitates the subsequent drawing of the coated wire to reduce the coated wire to the desired dimensions.
  • the diffusion step which is typically conducted at temperatures within the range of about 450 to 500°C, may cause a reduction in the tensile strength of the coated steel wire. The reduction can be of as much as 5% of the original tensile strength of the material. This tensile strength reduction impairs the effectiveness of the wire when used in the intended reinforcing application, particularly when used as a reinforcing component in motor vehicle tires.
  • U.S. Patent No. 4,486,477 discloses a ferrous wire having a homogeneous coating of nickel and copper. The wire is drawn, then is thermally softened, and is pickled before entering an electrolytic bath of copper and zinc cyanide. After the homogeneous coating is deposited, the coated wire is drawn to the desired dimensions.
  • U.S. Patent No. 4,828,000 discloses a steel substrate with a brass covering layer to enhance adhesion to the rubber, wherein the covering layer has on its surface a ratio Cu/(Cu + Zn) of no more than 0.2.
  • the reduction of copper percentage at the surface is obtained by heating the coated metal in an inert atmosphere to a temperature of between 250°C and 350°C.
  • JP 58-61297 discloses a method of plating a steel wire for tyre cord purposes. The method provides that copper plating and zinc plating are repeated alternatively at least twice on the steel wire, the outermost plating layer being copper. The plated wire is then drawn and the plated layers are thus converted to brass by diffusion of the copper and zinc during the drawing process.
  • the present invention relates to a method according to claim 1 and to a wire according to claim 5.
  • Dependent claims 2-4 and 6-9 address preferred features of the invention.
  • a coated metal wire is produced that provides significant advantages over prior art products of this type, particularly when employed as a reinforcing component in an elastomeric compound material of the type used in the construction of motor vehicle tires.
  • the elastomeric compound material may be an elastomer of either natural or synthetic origin having rubber-like characteristics, comprising fillers such as carbon black and silica are added.
  • the bonding is facilitated by increasing the concentration of copper at the reaction surface of the brass coating.
  • the concentration of copper at the reaction surface can be controlled according to the invention to match the characteristics of the elastomeric compound material being used, by selecting a composition and thickness of the most external deposited layer.
  • the drawability of the coated wire is improved. Specifically, this results when the crystallographic structure of substantially all of the brass coating is the face centered cubic alpha phase with only minor amounts and preferably trace amounts of the body centered cubic beta phase. It has been determined that the face centered cubic alpha phase is significantly more deformable than the body centered cubic beta phase, and thus the predominance of this former phase facilitates the wire drawing operation.
  • a tin-coated metal wire which is particularly adapted for drawing to form a brass surface coating thereon, is provided with at least three alternate alloying layers, each being of copper or zinc.
  • the most external of these layers is, however, of copper.
  • the most internal of the at least three layers is also of copper.
  • the wire onto which these layers are deposited is preferably steel.
  • the number of alternate alloying layers is preferably within the range of 3 to 5.
  • the alloying layers may consist essentially of, in weight percent, about 60 to 72 copper and balance zinc, preferably about 70 copper and about 30 zinc.
  • the metal wire may have a diameter of about 0.8 to 3.0 mm with the alloying layers in combination having a thickness of about 0.75 to 4.0 microns.
  • the thickness of the most external layer of copper is preferably about 0.1 to 0.5 microns.
  • the thickness of the most external copper layer could be selected to obtain a desired copper concentration on an outer surface of the coated metal wire.
  • the brass coating on the drawn wire preferably has a copper content of the outer surface greater than a copper content of any remaining portion of the brass coating.
  • the brass coating preferably consists essentially of, in weight percent, about 60 to 72 copper and balance zinc, more preferably about 70 copper and about 30 zinc.
  • the drawn wire preferably has a diameter of about 0.12 to 0.8 mm, with the brass coating having a thickness of about 0.1 to 0.3 microns.
  • the brass coated wire in accordance with the invention, may be contained as a reinforcing element within an elastomeric article, such as a motor vehicle tire.
  • the brass coating is chemically bonded to the elastomeric article by disulfide bonds formed between the brass coating and the composition of the elastomeric article.
  • the elastomer of the compound material may be of either natural or synthetic origin.
  • a brass coated metal wire is produced by depositing on a tin-coated metal wire at least three alternate alloying layers each being one of copper or zinc. The most external and most internal of the layers are copper. This coated wire is then subjected to a drawing operation which produces high temperature and pressure to alloy the copper and zinc layers and form the desired brass layer.
  • the metal of the wire is preferably steel and the number, composition and thickness of the deposited layers are as set forth above. These alloying layers may be deposited by electro-deposition.
  • sample BL2R80 was produced according to the invention, but utilizing only a first deposited layer of copper, and a second deposited layer of zinc.
  • pH 2 - 4, preferably 3
  • This bath is preferably designed to deposit copper on the previously deposited zinc layer.
  • pH - 8.6-8.9 preferably 8.7 g/l
  • a copper layer is always deposited as the outermost layer, to provide a greater copper concentration near the outer surface of the brass coating for the metal wire.
  • the outermost layer is preferentially copper, because it improves bonding of the wire with the elastomeric compound, as described above, and because an outer zinc layer tends to more rapidly wear the die of the drawing machine.
  • Preferential embodiments of the present invention include deposition of three or five layers as described above. Seven or more layers may also be deposited, however the electro-deposition steps become considerably more complicated as the number of layers increases.
  • the drawing operation reduces the diameter of the metal wire coated with copper and zinc layers.
  • the diameter reduction can be, for example, from a starting diameter of 0.8 to 3.0 mm to a final diameter of 0.12 to 0.8 mm.
  • the starting alloying layers in combination having a thickness of 0.75 to 4.0 microns, and after the drawing operation the brass coating having a thickness of 0.1 to 0.3 microns.
  • the thickness of the most external layer of copper is preferably 0.1 to 0.5 microns.
  • the thickness of the most external copper layer could be selected to obtain a desired copper concentration on an outer surface of the coated metal wire.
  • the plated wire is drawn to the final diameter by a drawing machine having a plurality of die passages, for example, 19 or 20, in order to obtain a reduction of the wire section between 10% and 12% through each die passage.
  • the speed of the wire at the output of the die is between 16 and 20 m/s.
  • the angle between the wire and the die is about between 8° and 12°.
  • a water emulsion of lubricant (of the type well known to one skilled in the art) is used to reduce friction and cool the system.
  • the pressure acting on the wire and coating in the die is approximately 1000 to 1500 MPa, as computed from the drawing force and the surface area of the die.
  • the mean value of temperature to which the wire is subjected is approximately 150 Deg. C, calculated from the wire speed and other parameters. However, peak values of temperature in the die may be much higher and can reach hundreds of degrees Celsius.
  • the efficiency of the system is measured by counting the number of breakages occurring, and by measuring the amount of brass loss during drawing. Generally, a normal brass loss is about 5%-18% by weight from the starting amount.
  • Table 2 shows the results of drawing of the plated wire produced as described above. TABLE 2 - Drawing Ability of Samples (Speed 16 m/s; Emulsified Lubricant) Sample Wire Produced (kg) Number of Breakages % Loss of Brass from Starting Amount BL3N6535 60 - 10.7 BL3R4040 40 - 13.5 BL2R80 40 1 26
  • sample BL2R80 which only has two layers, the innermost layer being of copper and the outermost layer of zinc, has shown an inferior performance compared to the other samples.
  • the crystallographic phases of interest that are present in the alloy are the ⁇ phase, the ⁇ phase and the ⁇ phase.
  • the drawn brass coating is characterized by a face centered cubic alpha ( ⁇ ) phase structure with only trace amounts of the body centered cubic gamma ( ⁇ ) and beta ( ⁇ ) phases, which are difficult to deform in contrast to the easy deformability of the face centered cubic alpha phase.
  • ⁇ body centered cubic gamma
  • beta ( ⁇ ) phases which are difficult to deform in contrast to the easy deformability of the face centered cubic alpha phase.
  • the presence of only alpha phase in the brass alloy, with only traces of the beta and gamma phases results in good drawing characteristics of the brass coated metal wire.
  • One technique used to evaluate the drawn brass coated wire is Auger spectroscopy. This technique gives the atomic concentration profile for the elements present in the coating.
  • the elements present were zinc, copper, iron, and oxygen.
  • the average concentration of copper and zinc at the surface of the coating is related to the expected reactivity between the cords and the elastomeric compound material. The greater the copper concentration, the greater the reactivity.
  • the concentration profile of the elements present in one of the samples of drawn coating is shown in the Auger spectrographic analysis presented in Figure 1 .
  • the y-axis represents the atomic concentration profile of specific elements with respect to the total concentration
  • the x-axis represents the sputtering time (in minutes) corresponding to the time during which the wire was exposed to Argon ions bombardment.
  • the sputtering time is proportional to the penetration of Argon ions in the alloy, and therefore indicates the depth from the surface of the wire where the analysis takes place.
  • We can see in this figure that in a small portion near the surface of the wire, near t 0, there is a large number of oxides, due to the oxidation by contact with air.
  • the concentration of copper is high near the surface and is decreasing in a continuous way as we move deeper in the wire.
  • the drawn coated wire is used to form cords suitable for reinforcing the elastomeric compound material.
  • the brass plated wires may be stranded to obtain various cord constructions, each optimized for a specific use.
  • the cord may be composed by a different number of wires with various diameters. In the following examples, a 3 x 0.22 cord is used, formed from 3 wires of 0.22 mm diameter. The cords were then tested to evaluate their characteristics.
  • the expected reactivity of the cord formed by the drawn coated wires can be measured by subjecting the cord to a sulphidization reaction. This reaction simulates the adhesion reaction between the metal surface and the elastomeric compound material.
  • a sample of the cord is immersed in a solution of sulfur in xylene at the boiling point (138 Deg. C.) The sample is then analyzed using Auger spectroscopy to measure the sulfur content present. A high ratio of sulfur to copper indicates high reactivity, and a low ratio indicates low reactivity.
  • Figure 2 shows the Auger spectroscopy results for the same sample shown in Fig. 1 , but after the sulphuring reaction.
  • the relative reactivity of different sample cords can be compared after sulphidization by measuring the sulfur to copper ratio for each sample, as described above. Table 3 shows this comparison for some of the samples described in Table 1. The relative reactivity is obtained by defining the reactivity of sample BL3N6535, which is the most reactive as being equal to 100. The other samples have a lower reactivity, ranging between 50 to 80% of the reactivity of sample BL3N6535. TABLE 3 - Reactivity of Cord Samples Sample Reactivity (Relative Speed of sulphidization) BL3N6535 100 BL3R4040 70 BL3R6020 60 BL3R7010 50 BL3N8515 80 BL3N2525 80 BL3N3515 70
  • the metal wire upon which the layers of copper and zinc are deposited is a steel wire. More preferably, the steel wire has one of the compositions described in Table 4. TABLE 4 - Composition of Steel Wire ELEMENT STEEL 0.7%C STEEL 0.8%C STEEL 0.9%C C 0.735 0.810 0.896 Si 0.229 0.227 0.227 Mn 0.479 0.480 0.416 P 0.009 0.006 0.007 S 0.008 0.006 0.006 Cr 0.028 0.028 0.019 Mo 0.003 0.001 0.001 Ni 0.016 0.022 0.019 Al 0.001 0.001 0.001 Cu 0.009 0.009 0.009 0.009
  • an additional layer of material is deposited on the metal wire before the copper and zinc layers are deposited, prior to drawing the metal wire.
  • a layer of tin is deposited as a first, or innermost layer on the metal wire prior to the deposition of the copper and zinc layers.
  • Tin possesses excellent corrosion resistance properties, and can thus provide higher corrosion resistance to the drawn coated wire.
  • the deposition of tin on the metal wire can be performed by electro-deposition, with a bath as follows:
  • Brass is intended to include copper based alloys of copper, zinc, and small amounts of additional metals, such as tin.
  • the alloy resulting from drawing the wire with the deposited layers described above, according to this embodiment, in a preferred embodiment has the following composition:
  • the wire can be used to reinforce various types of elastomeric articles, such as tires, hoses, or belts.
  • the metal wire is used as reinforcing metallic cord, in particular, in elastomer-matrix composite articles of manufacture, specifically in pneumatic tyres for motor-vehicles, according to the present invention.
  • a tyre for vehicle wheels comprises a carcass of toric form having a crown region, two axially opposite sidewalls terminating at a radially internal position with corresponding beads for anchoring of the tyre to a corresponding mounting rim, said beads being each reinforced with at least one annular metal core, usually referred to as bead core, said carcass comprising at least one rubberized-fabric ply having its ends turned over around said bead cores, and optionally other reinforcing elements such as flippers, strips and bands of rubberized fabric.
  • Said carcass further has a tread band disposed crownwise and moulded with a raised pattern designed to get in contact with a roadway while the tyre is running, and a belt structure, interposed between said tread band and said at least one carcass ply and comprising one or more rubberized-fabric strips reinforced with textile or metallic cords differently inclined in the corresponding strips, relative to the circumferential direction of the tyre.
  • the elastomeric articles can include known types of natural or synthetic rubber, including fillers and additives that are known in the art.
  • the elastomeric article can be made of a polymeric base natural and/or synthetic), carbon black, ZnO, stearic acid, antioxidants, anti-fatigue agents, plasticizers, sulphur, accelerating agents.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ropes Or Cables (AREA)
  • Reinforced Plastic Materials (AREA)

Claims (9)

  1. Verfahren zum Herstellen eines Kupferbasislegierungbeschichteten Metalldrahts, der speziell zur Verwendung in drahtverstärkten elastomeren Gegenständen ausgebildet ist, das umfasst: auf einem Metalldraht Aufbringen von mindestens drei wechselnden Nicht-Legierungsschichten, die jeweils aus Kupfer oder Zink ausgebildet sind, wobei eine äußerste der Nicht-Legierungsschichten Kupfer ist, und Ziehen des Drahts zum Legieren der Nicht-Legierungs-Kupfer- und Zinkschichten zum Bilden von Kupferbasislegierung, dadurch gekennzeichnet, dass es ferner umfasst: vor dem Aufbringen der Nicht-Legierungsschichten aus Kupfer und Zink, die Schritte des Anbringens einer korrosionsresistenten Schicht aus Zinn.
  2. Verfahren nach Anspruch 1, das einen vorbereiteten Schritt des Auswählens umfasst, dass der Metalldraht Stahl ist.
  3. Verfahren nach Anspruch 1, bei dem die wechselnden Nicht-Legierungsschichten durch elektrolytische Abscheidung aufgebracht werden.
  4. Verfahren nach Anspruch 1, bei dem das Ziehen des Metalldrahts das bei einer Geschwindigkeit von zwischen 16 und 20 m/Sek Führen des Drahts durch zwischen 19 und 20 Ausformwerkzeugdurchgänge umfasst.
  5. Gezogener Metalldraht, der nach dem Verfahren gemäß einem der Ansprüche 1 bis 4 hergestellt wurde, der insbesondere zur Verwendung in drahtverstärkten elastomeren Verbundgegenständen ausgebildet ist, wobei der Metalldraht darauf eine Kupferbasislegierungsoberflächenbeschichtung aufweist, wobei die Kupferbasislegierungsoberflächenbeschichtung eine äußere Fläche und eine innere Fläche aufweist, wobei ein Kupfergehalt der äußeren Fläche größer ist als ein Zinkgehalt der äußeren Fläche, dadurch gekennzeichnet, dass die innere Fläche der Kupferbasislegierungsbeschichtung Zinn enthält.
  6. Gezogener Metalldraht nach Anspruch 5, wobei der gezogene Metalldraht ein Stahldraht ist.
  7. Gezogener Metalldraht nach Anspruch 5, bei dem die Kupferbasislegierungsbeschichtung in Gewichtsprozent im Wesentlichen aus 60 bis 72 Kupfer und Restzinn besteht.
  8. Gezogener Metalldraht nach Anspruch 5, wobei der gezogene Metalldraht einen Durchmesser von 0.12 bis 0.8 mm aufweist, und die Kupferbasislegierungsbeschichtung eine Dicke von 0.1 bis 0.3 µm (Micron) aufweist.
  9. Gezogener Metalldraht nach Anspruch 5, bei dem die Kupferbasislegierungsbeschichtung in Gewichtsprozent im Wesentlichen aus 2 bis 13 Zinn, 23 bis 34 Zink und 59 bis 73 Kupfer besteht.
EP99121011.3A 1998-10-28 1999-10-21 Beschichtete Metalldrähte und Herstellungsverfahren Expired - Lifetime EP1004689B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99121011.3A EP1004689B1 (de) 1998-10-28 1999-10-21 Beschichtete Metalldrähte und Herstellungsverfahren

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP98120359 1998-10-28
EP98120359 1998-10-28
EP99121011.3A EP1004689B1 (de) 1998-10-28 1999-10-21 Beschichtete Metalldrähte und Herstellungsverfahren

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EP1004689A2 EP1004689A2 (de) 2000-05-31
EP1004689A3 EP1004689A3 (de) 2001-11-28
EP1004689B1 true EP1004689B1 (de) 2014-01-29

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60205834T2 (de) 2001-09-20 2006-05-18 Sumitomo Electric Industries, Ltd. Methode zu Herstellung beschichteter Metalldrähte
DE602005020622D1 (de) * 2004-07-05 2010-05-27 Sumitomo Sei Steel Wire Corp Wulstkord für einen pneumatischen reifen
TR201810002T4 (tr) * 2010-12-23 2018-08-27 Bekaert Sa Nv Bir çelik telin sürekli olarak üretilmesine yönelik proses ve teçhizat.
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5192739A (en) * 1975-02-13 1976-08-14 Tairyukaseito taisumatsujiseino suguretadenkiburiki
JPS6057520B2 (ja) * 1981-10-05 1985-12-16 住友電気工業株式会社 タイヤコ−ド用鋼線のめつき方法

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EP1004689A3 (de) 2001-11-28

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