• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention concerns a metal wire, used to produce reinforcing elements for articles of elastomeric material, which is provided with a coating able to ensure at the same time a good resistance to corrosion, good values of initial adhesion and a low decay, due to ageing, of the bond with the elastomeric material, said coating being formed by two concentric layers of a Zn/Ni alloy, where the radially inner layer contains Zn in an amount ranging between 60% and 90% on the layer total and the radially outer layer contains Ni in an amount ranging between 60% and 80% on the layer total.
    公开号:SU1662345A3
    申请号:SU884355296
    申请日:1988-03-01
    公开日:1991-07-07
    发明作者:Й.ван Оэй Вим
    申请人:Пирелли Координаменто Пнеуматики, С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a metal wire having an anti-corrosion coating capable of providing very good adhesion to elastomer materials, in particular to stainless steel wire, which is used to produce well-known cords used to strengthen products made from elastomeric materials, for example pneumatic tires, conveyor belts, belts gears.
    The purpose of the invention is to improve the quality by increasing the corrosion resistance of the wire.
    Of all the tested alloys, the most interesting are the alloys,
    consisting of zinc and nickel or zinc and cobalt. Replacing copper with zinc or cobalt contributes to a not so much deterioration in adhesion properties as it ages, however, the problem of maximizing adhesion and at the same time resistance to corrosion is left unresolved.
    From the point of view of the composition of the alloys, these two characteristics appear to be in some contradiction: an increase in the percentage metal content (for example, Ni) improves one characteristic (in this case, the coupling by an elastomeric material), but causes the deterioration of the other. Thus, in the course of research can be
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    only a compromise solution was found that best suits both requirements.
    Metal wire for hardening products from elastomeric materials has an anti-corrosion coating and is suitable for adhering to an elastomeric material in which it is embedded, while the coating is made of an alloy of zinc and nickel or cobalt and consists of two concentric layers located in radial section one above the other, each layer made of Zn / Ni alloy, or cobalt, and the layer with the highest percentage of Zn is internal (in the radial section).
    The zinc content in the inner radial section varies from 60 to 90%. The difference between the percentage concentrations of nickel in the two superimposed layers should be at least 20%. In both layers, the difference between 100% and the percentage of this metal corresponds to the concentration (of the second metal in the alloy.
    Metal wire is pulled up to a diameter of 0.12-0.5 µm and is used in the form of beams for the manufacture of cord cords used as reinforcing elements, mainly in rubberized materials.
    Mentioned wire, which has a larger end diameter, is covered with a first protective layer of an alloy of nickel and zinc or cobalt containing from 60 to 90% zinc, the remaining fraction of which is nickel. This layer will contain other metals in the form of impurities, i.e. in such small quantities that their percentage concentrations are insignificant.
    The application of said alloy in an electrolytic bath using standard methods can be carried out in two different ways. The first method is that zinc and nickel (or cobalt) are applied to the wire separately, in turn, and the formation of the Zn / Ni alloy (or cobalt) occurs as a result of mutual diffusion of metals, caused by an appropriate heat treatment, t . by heating the wire.
    g Q 5
    Q 5
    35
    0
    50 55
    0
    45
    The first coating layer, which serves to protect the wire from corrosion, contains 70% Zn and 30% Ni.
    An alternative method involves the simultaneous deposition of metals in the required amounts in the same electrolytic bath. In this case, immediately get the wire coated with the desired alloy.
    The parameters of one of the possible modes of conducting the process in an electrolytic bath are as follows:
    Limits of change
    temperatures, ° C 10-30
    The range of change of pH 4-8
    Limits of change
    current density
    A / dm 250-30
    NiSO (hexohydrate
    Nickel sulfate, g / l 170
    ZnSO (sulfate,
    zinc), g / l10
    CV03 (borax), g / l 10
     (ammonium chloride), g / l14
    NaC H-jj-O. (sodium lauryl sulfate), g / l 1
    The thickness of the first layer, regardless of how it is applied, is 0.25-2 microns. The wire thus treated is then covered with a second layer also of Zn / Ni alloy, which in terms of the percentage of metals is an inverse version of the first layer, i.e. its nickel content is 60-80%, with the remaining 100% of zinc; it does not take into account the presence of already mentioned impurities. In any case, it is desirable that the difference in the percentage nickel concentrations in the two superimposed layers be at least 20%.
    When forming the second layer, the deposition of two metals cannot be carried out separately in two successive steps. The process of applying the second layer should be one-step, i.e. two metals should be precipitated simultaneously. Otherwise, heat treatment, necessary for the formation of an alloy as a result of the diffusion of two metals, can also affect the already deposited inner layer, which can cause diffusion of all metals included in the composition of the alloys. As a result of this phenomenon, the formation of one uniform layer is possible, which contradicts the invention.
    If the layer is applied in one stage, then the only possible means is to use an electrolytic bath, the composition of which and process conditions are as follows:
    Limits of change
    temperature, 0 C 60 Limits of change pH 4 Limits of change
    current density, A / dm2
    NiS04, g / l
    ZnSO, g / l H3BO ,, g / l NH4C1, g / l KaS ,,
    G / L
    with
    170 1
    10 114
    one
    80 8
    thirty
    The thickness of the second layer is 0.25-2 microns. In addition, it is desirable that the total thickness of the coating, which folds from the thicknesses of both layers, is 0.5-4 µm. The thickness of each layer and the total thickness of the coating must be determined when the wire is removed from the electrolytic bath, i.e. before carrying out any operations that may lead to a change in these parameters, in particular, before the start of stretching. After the coating layers are applied to the wire in the manner described and the characteristics required for it are achieved, the wire diameter is adjusted to the desired final value by means of one or several stretches.
    j Thus, a wire coated with two radially overlaid concentric layers of Zn / Ni alloy, or cobalt, is obtained, each of which performs different functions: the inner, deeper layer serves to protect against corrosion, and the upper layer - to improve adhesion with the elastomer material.
    The offered wire in comparison with the known ones is characterized by higher quality indicators.
    Example 1. Wire produced by the proposed method using two successive procedures for the simultaneous deposition of Zn and Ni in electrolytic baths and subsequent drawing it to the required diameter of 0.175 mm, having a coating (coating 1) consisting of an inner in a radial cut a layer with a thickness of 0.1 mm, which is formed from.
    five
    0
    five
    0
    five
    an alloy containing 70% Zn and 30% Ni, and a radially outer layer with a thickness of 0.1 mm, formed from an alloy containing 70% Ni and 30% Zn, kept in a climate chamber at a temperature of 45 ° C and a relative humidity of 90% . A commonly used wire of the same diameter with a coating (coating 2) consisting of one alloy layer containing, respectively, 35% Zn and 65% Cu 0.2 µm thick, which was applied by traditional methods, was also kept in a medium with the same conditions.
    The tensile strength of wire specimens was measured at certain intervals during their stay in the described conditions, which were created to stimulate rapid corrosion with the formation of rust. The percentage reduction in tensile strength can be considered as an indicator of the corrosion process.
    The percentage reduction in strength was calculated using the following formula: TS (initial TS - final TS) / initial, where TS is the reduction in tensile strength,% / TS is the tensile strength.
    The results obtained in Table 1 were obtained. one.
    From tab. 1 shows that the corrosion resistance of wire samples, which were coated with the proposed method, is much higher.
    Example 2. The test described in example 1 was carried out with samples of wire having a diameter of 0-25 mm, which was coated with a thickness of 0.25 µm. This coating according to the invention consisted of two concentric layers with a thickness of 0.125 µm each.
    The results obtained in the table. 2
    0
    In this case, wire samples having the proposed coating also showed higher corrosion resistance.
    Example 3. This test was tested to determine the adhesion of cords with dimensions 7x4x0.175S made of wire9 described in Example 1 with respect to rubber materials after vulcanization and the detection of adhesion changes over time in high temperature conditions.
    and at appropriate relative humidity values.
    The test material (A and B) had the following composition, presented in table. 3
    The adhesion was tested by measuring the force required to remove the cord from a small cylinder from vulcanized rubber using a known method (Kautschuk und Gummi Kunststoffe, v.5, 1969, pp. 228-232). The samples were heat treated for 30 min at a temperature of 151 ° C, the magnitude of the pulling force was measured using an electronic dynamometer. The thickness of the rubber layer covering the cord extracted from the sample was evaluated by comparison with standard samples and was characterized by a coating index that indicates how much (as a percentage) of the total surface of the cord remains substantially covered by rubber. In the case when the index of the coating was high, the separation of the cord from the material was due to the insufficient cohesion of the latter, and not due to the weak adhesion on the metal / / rubber boundary surface. The samples were kept in a climatic chamber with a temperature of 65 ° C and a relative humidity of 90%. The results are shown in Table. 4 (PF is the pulling force in newtons, C1 is the value of the coverage index in percent),
    The results indicate a clear improvement in the stability of the adhesion characteristics over time for cords made of wire having the proposed coating.
    Example 4. The tests were carried out according to the scheme described in example 3, however, cords with dimensions of 2-2 0.25 were used from the wire samples described in example 2. The results obtained are given in table. five.
    The results obtained in the experiments with this cord also indicate a significantly less weakening of adhesion as the material ages in those samples that were made of wire coated with two layers of Ni / Zn alloy according to the proposed method.
    In an alloy (Zn / Ni or Co), the percentage of complementary metals can vary widely, forms coatings more compact than in the case of copper, and are non-porous.
    0
    five
    0
    five
    0
    five
    In addition, the zinc removal process is significantly slower compared to Cu / Zn alloys.
    权利要求:
    Claims (4)
    [1]
    1. Metal wire for strengthening products made of elastomeric material, having a corrosion-resistant coating and suitable for adhesion with an elastomeric material, into which said wire is introduced, characterized in that, in order to improve quality by increasing the resistance of the wire to corrosion, its corrosion-resistant coating made in the form of two highly concentrated layers of an alloy of two metals, one of which is zinc, and the other is nickel or cobalt, the inner layer of which contains 60-90% zinc, and Normal - 60–80% of another metal, with the difference in the percentage of another metal in the inner and outer layers being at least 20%.
    [2]
    2. Wire pop. 1, characterized in that the total thickness of the coating does not exceed 4 microns.
    [3]
    3. Wire according to claim 1, characterized in that the thickness of the inner layer in the radial section is 0.25-2 microns.
    [4]
    4. Wire according to claim 1, characterized in that the thickness of the outer radial section of the layer is 0.25-2 microns.
    Table 1
    类似技术:
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    US5338620A|1994-08-16|Metal wire with a layer of coating for reinforcing articles made of elastomeric materials, and articles made of elastomeric materials reinforced with the said wire
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    同族专利:
    公开号 | 公开日
    CN88101089A|1988-10-05|
    EP0283738B1|1992-06-03|
    CN1012829B|1991-06-12|
    EP0283738A1|1988-09-28|
    IT8719541D0|1987-03-02|
    AT76907T|1992-06-15|
    KR910006215B1|1991-08-17|
    JPS63277792A|1988-11-15|
    IT1225871B|1990-12-07|
    KR880011382A|1988-10-28|
    US4911991A|1990-03-27|
    DE3871574D1|1992-07-09|
    DE3871574T2|1993-01-21|
    BR8800969A|1988-10-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1984335A|1931-08-12|1934-12-11|Indiana Steel & Wire Company|Metal coated ferrous article and process of making it|
    US2038551A|1934-10-31|1936-04-28|Nat Standard Co|Method of electroplating zinc on cadmium zinc alloys|
    US2296838A|1937-11-01|1942-09-29|Nat Standard Co|Rubber adherent metal|
    BE571418A|1955-09-23|
    US4265678A|1977-12-27|1981-05-05|Tokyo Rope Mfg. Co., Ltd.|Metal wire cord|
    US4226918A|1978-08-03|1980-10-07|National-Standard Company|Rubber adherent ternary Cu-Zn-Ni Alloy coated steel wires|
    FR2445764A1|1979-01-05|1980-08-01|Bekaert Sa Nv|NOVEL ELEMENTS BASED ON STEEL THREADS FOR REINFORCING RUBBER COMPOSITIONS|
    JPS5845365B2|1979-12-05|1983-10-08|Bridgestone Tire Co Ltd|
    JPS6136078B2|1980-10-17|1986-08-16|Kobe Steel Ltd|
    JPS6323278B2|1981-07-03|1988-05-16|Kawasaki Steel Co|
    DE3414048A1|1984-04-13|1985-10-17|Nisshin Steel Co., Ltd., Tokio/Tokyo|METHOD FOR PRODUCING STEEL PARTS GALVANIZED WITH A ZINC-NICKEL ALLOY|
    US4659631A|1984-05-17|1987-04-21|Sumitomo Metal Industries, Ltd.|Corrosion resistant duplex plated sheet steel|
    GB8500323D0|1985-01-07|1985-02-13|Bekaert Sa Nv|Steel reinforcing elements|
    JPS6233793A|1985-08-05|1987-02-13|Usui Internatl Ind Co Ltd|Corrosion resistant superposedly coated steel products|GB2230537B|1989-03-28|1993-12-08|Usui Kokusai Sangyo Kk|Heat and corrosion resistant plating|
    IT1251401B|1991-09-09|1995-05-09|Pirelli|METALLIC WIRE WITH DOUBLE COATING LAYER FOR THE REINFORCEMENT OF ELASTOMERIC ITEMS AND ARTICLES IN ELASTOMERIC MATERIALS REINFORCED WITH THAT WIRE.|
    JP2899465B2|1991-12-16|1999-06-02|東京製綱株式会社|Method of manufacturing steel wire for rubber reinforcement|
    IT1273334B|1994-02-24|1997-07-08|Pirelli|METALLIC WIRE SURFACE TREATED TO MAKE IT SUITABLE FOR USE IN ELASTOMERIC COMPOSITE ELEMENTS AND PROCEDURE FOR ITS REALIZATION|
    US6120911A|1997-09-09|2000-09-19|The Goodyear Tire & Rubber Company|Zinc-rich coated steel article|
    DE19837431C2|1998-08-18|2001-10-31|Schloetter Fa Dr Ing Max|Coating hardened steel or cast iron components and method of applying same|
    BR9904763B1|1998-10-28|2010-02-23|process for producing a metal wire, and metal wire, used as a reinforcement element in tires.|
    US20060121302A1|2004-12-07|2006-06-08|Erickson Gary C|Wire-arc spraying of a zinc-nickel coating|
    US20060222880A1|2005-04-04|2006-10-05|United Technologies Corporation|Nickel coating|
    DE102011102780B4|2011-05-30|2013-02-28|Anvis Deutschland Gmbh|Elastic coupling part, erosion assembly and method of making the elastic coupling part|
    US9521881B2|2013-04-15|2016-12-20|Joran Bachtold|Flexible accessory holder|
    JP6204953B2|2015-09-18|2017-09-27|矢崎総業株式会社|Electric wire with terminal and wire harness using the same|
    CN107824630B|2017-10-23|2019-05-10|江苏兴达钢帘线股份有限公司|A kind of metal wire, its manufacturing method and tire|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT8719541A|IT1225871B|1987-03-02|1987-03-02|METAL WIRES IMPROVEMENTS FOR ELASTOMERIC MATERIALS REINFORCEMENT|
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