JP5235433B2 - Al plated steel wire and manufacturing method thereof - Google Patents

Al plated steel wire and manufacturing method thereof Download PDF

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JP5235433B2
JP5235433B2 JP2008021472A JP2008021472A JP5235433B2 JP 5235433 B2 JP5235433 B2 JP 5235433B2 JP 2008021472 A JP2008021472 A JP 2008021472A JP 2008021472 A JP2008021472 A JP 2008021472A JP 5235433 B2 JP5235433 B2 JP 5235433B2
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steel wire
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JP2009179865A (en
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忠昭 三尾野
真一 鴨志田
保徳 服部
剛 清水
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日新製鋼株式会社
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  The present invention relates to an Al-plated steel wire having an Al-plated coating layer on the surface of a steel core wire, and particularly relates to an Al-plated steel wire suitable for a conductive member (element wire) such as an automobile wire harness and a method for producing the same.

  An automobile wire harness is composed of a large number of conductors, and each conductor is made by bundling several to several tens of “elements”. In recent years, there has been an increasing need for weight reduction and compactness, and there is an increasing demand for thinning wire harnesses. In addition, in order to eliminate the need for separate collection work at the time of car disassembly, a wire harness for a wire harness having a highly recyclable structure has been strongly desired.

  Each conducting wire constituting the wire harness is often fastened to the terminal by “caulking”, and each element wire is required to have a certain strength so as not to be easily broken at the caulking portion. It is necessary to secure a wire diameter of about 0.3 mm or more in the case of a Cu wire and 1 mm or more in the case of an Al wire for a current wire harness for a signal wire harness. If it is thinner than that, breakage at the “caulking portion” tends to be a problem due to insufficient strength.

  From the viewpoint of recyclability, Al, which can be dissolved together with iron scrap, is superior to Cu, which is an inhibitory element for iron recycling. In terms of electrical conductivity, Al has a larger volume resistivity than Cu, but in the case of a signal wire harness that allows a weak current to flow, there is no problem with Al strands. However, the Al wire has to employ a thick wire diameter in order to solve the shortage of strength as described above, and cannot fully meet the needs for compactness.

  On the other hand, in applications requiring high strength and high corrosion resistance, Al-plated steel wires having steel wires as core wires are known (Patent Documents 1 and 2). Patent Document 1 describes an Al-plated steel wire used for wires for fishing net ropes, power line reinforcement, submarine optical fiber cable reinforcement, and the like. The steel wire disclosed in the example of Patent Document 1 is as thick as 2 to 13 mm in wire diameter, and the purpose of Al plating is to improve corrosion resistance. The Al-plated wire of Patent Document 2 is for high-strength bolts, and FIG. A low-resistance and small-diameter Al-plated steel wire that can be used as a wire of a wire harness has not yet been realized.

  When hot-dip Al plating is applied to a steel material, a treatment for activating the steel surface is usually performed as a pretreatment. As the activation method, a flux method and a gas reduction method are generally used. In the flux method, a steel material is immersed in a flux mainly composed of sodium chloride, zinc chloride or the like. This method is easy to apply to steel plates and steel wires with relatively large wire diameters, but in the case of thin steel wires with a wire diameter of, for example, 1 mm or less, it is difficult to attach flux to the entire steel wire. is there. In addition, white smoke is often generated, and equipment such as ventilation is very expensive. On the other hand, in the gas reduction method, the steel material is exposed to a high temperature reducing atmosphere mainly composed of nitrogen and hydrogen before being immersed in the plating bath, and the surface is heated and reduced. This technique is difficult to apply in the case of a thin steel wire having a wire diameter of, for example, 1 mm or less, because the strength of the steel wire is lowered by high-temperature heating and may break. Thus, it is not easy to apply Al plating to a steel wire having a small diameter suitable for the wire of the wire harness by a conventional general method.

Japanese Patent Laid-Open No. 3-219005 JP 2004-360022 A

  The present invention is intended to provide a thin wire suitable for a wire of a wire harness, having high strength and low resistance, and excellent in recyclability.

In order to achieve the above object, in the present invention, a molten Al plating layer is provided on the surface of a steel core wire having a diameter (equivalent circle diameter) of 0.1 to 0.5 mm via an Fe-Al alloy layer. Al-plated steel wire, in a cross section perpendicular to the longitudinal direction,
(1) The segmented Fe-Al alloy phase is dispersed in the molten Al plating layer, and the total area ratio of the segmented Fe-Al alloy phase in the molten Al plating layer is 40% or less. ,
(2) The area ratio of the molten Al plating layer occupying the entire cross section (including the fragmented Fe-Al alloy phase dispersed therein) is 30% or more.
An Al plated steel wire is provided.

Here, when the cross-sectional area of the steel wire present in the cross section perpendicular to the longitudinal direction of the Al-plated steel wire S (mm), the circular constant [pi, D defined by S = πD 2/4 (mm ) Is called the equivalent circle diameter of the steel core wire. The “molten Al plating layer” is a plating layer formed by dipping in a molten Al plating bath having a Si content of 0 (no addition) to 15 mass%. Both the Fe-Al alloy layer and the fragmented Fe-Al alloy phase are alloy phases having a composition relatively close to the θ-phase or η-phase of the Fe-Al alloy, and when the plating bath contains Si. Usually, Si is also contained in these alloy phases. The composition of the Fe—Al based alloy layer and the piece-like Fe—Al based alloy phase are not necessarily close to each other. As a result of the investigation, there is a tendency that the Al concentration is higher in the fragmented Fe-Al alloy phase.

In addition to (1) and (2) above,
(3) The Si content of the matrix portion excluding the fragmentary Fe-Al alloy phase in the molten Al plating layer is 9% by mass or less.
Al plated steel wire is a more suitable target.

In the present invention, in the Al plated steel wire, in particular, the electrical resistance ρ 1 (Ω / m) per unit length of the Al plated steel wire and the steel core wire (molten Al) constituting the Al plated steel wire. The ratio ρ 1 / ρ 0 of the electrical resistance ρ 0 (Ω / m) per unit length (assuming a state in which no plating is applied) is 0.55 or less.

Here, the electrical resistance ρ 0 per unit length of the steel core wire can be calculated from the value of the equivalent circle diameter D (mm) of the steel core wire and the volume resistance value of the steel core wire. In the actual measurement, for example, the Al plating layer of the Al plated steel wire is melted and removed, and only the steel core wire is taken out and measured. This ρ 0 can be regarded as substantially the same as the measured value of electrical resistance per unit length for the Zn-plated steel wire to be subjected to hot-dip Al plating.

  The Al-plated steel wire of the present invention can be obtained by subjecting a Zn-plated steel wire (a steel wire having a Zn-plated layer on the surface of the steel core wire) to hot-dip Al plating. At that time, by adjusting the immersion time in the Al plating bath, the “total area ratio of the fragmented Fe—Al-based alloy phase in the molten Al plating layer” in the above (1) and the above (2) The “area ratio of the molten Al plating layer in the entire cross section” can be controlled within a desired range. In addition to adjusting the immersion time, an adhesion amount control means such as electromagnetic wiping may be used in combination. As the Zn-plated steel wire, a steel wire that has been subjected to drawing after Zn plating may be employed.

  ADVANTAGE OF THE INVENTION According to this invention, the low resistance Al plating steel wire which ensured the sufficient amount of Al plating adhesion although it was small diameter was provided. Since this Al plated steel wire can be processed together with iron scrap, it is more recyclable than Cu wire. In addition, since it has higher strength than conventional Al strands, it is possible to ensure durability in the “caulking portion” or the like even if the diameter is reduced. Therefore, the Al plated steel wire of the present invention is suitable for a wire harness for automobile wire harness. In addition, since the Al-plated steel wire can be manufactured by directly performing hot-dip Al plating on the Zn-plated steel wire, pretreatment by the flux method or gas reduction method may be omitted in hot-dip Al plating. it can.

  In FIG. 1, the structure of a cross section perpendicular | vertical to the longitudinal direction in the Al plating steel wire of this invention is shown typically. A continuous Fe-Al alloy layer is formed on the surface of the steel core wire, and an Al plating layer is formed thereon. In the Al plating layer, a fragmented Fe-Al alloy phase is dispersed. In general, the Zn plating layer derived from the Zn-plated steel wire before the Al plating cannot be clearly identified in this cross section. In some cases, Zn can be detected in the Fe—Al alloy layer or the fragmented Fe—Al alloy phase.

  The Al-plated steel wire of the present invention can be produced by subjecting a Zn-plated steel wire to hot-dip Al plating. Since the steel material surface before Al plating is coated with Zn, it is possible to form a molten Al plating layer with good adhesion without performing a pretreatment by a flux method or a gas reduction method.

  Further, according to the study by the inventors, it is considered that the Zn plating layer that existed before the molten Al plating contributes to the formation of the fragmentary Fe—Al alloy phase. It has also been found that the formation of a piece-like Fe—Al alloy phase contributes to an increase in the amount of Al plating adhesion. Although these mechanisms have not been elucidated, the following may be considered.

  That is, when a Zn-plated steel wire is immersed in a molten Al plating bath, it is considered that the surface Zn melts rapidly and most of it is dissolved in the bath. However, some Zn enters the grain boundary from the surface of the steel core wire, and when Fe and Al react on the surface of the steel to form an Fe—Al alloy layer, the Fe—Al alloy layer It is thought that a part may be easily peeled off from the steel surface. It is considered that the peeled piece of the Fe—Al alloy layer forms a fragmented Fe—Al alloy phase. The thickness of the Zn plating layer of the Zn-plated steel wire to be subjected to hot-dip Al plating is generally in the range of 0.3 to 25 μm, preferably 1 to 15 μm, and more preferably 3 to 10 μm.

  In general, when hot dip plating is performed on a steel wire having a small wire diameter, it is difficult to ensure abundant plating adhesion, unlike the case of a steel wire or a steel wire having a large wire diameter. That is, when the steel wire is pulled up from the molten Al plating bath, after leaving the plating bath, the unsolidified Al lifted along with the steel wire is likely to flow down from the surface of the steel wire, resulting in Al adhering after solidification. The amount of plating layer tends to decrease. However, when a piece-like Fe-Al alloy phase is formed during immersion in the hot dipping bath or in the middle of pulling up from the hot bath, the molten Al is lifted along with the steel wire after leaving the plating bath. It is presumed that the fragmented Fe—Al-based alloy phase present therein has resistance to Al flow-off, and contributes to securing an abundant amount of plating even though the wire diameter is thin.

  In the Al-plated steel wire of the present invention, it is desirable that the diameter (equivalent circle diameter) of the steel core wire is adjusted to a range of 0.1 to 0.5 mm. If it is too thin, it will be difficult to sufficiently secure the strength of the wire harness. On the other hand, if it is too thick, the cross-sectional ratio of the Al plating layer is relatively reduced, and it becomes difficult to ensure sufficient conductivity as a wire of the wire harness. In addition, in order to adjust the diameter of a steel core wire, after performing Zn plating to a steel strand, the method of performing the wire drawing process by drawing | extracting suitably can be employ | adopted.

In this Al plated steel wire, it is important that the following two points are satisfied in the cross section perpendicular to the longitudinal direction.
(1) In the molten Al plating layer, the fragmented Fe—Al based alloy phase is dispersed, and the total area ratio of the fragmented Fe—Al based alloy phase in the molten Al plated layer is 40% or less. about.
(2) The area ratio of the molten Al plating layer (including the fragmented Fe-Al alloy phase dispersed therein) in the entire cross section is 30% or more.

As described above, the fragmentary Fe-Al alloy phase of (1) is necessary to secure a large amount of Al plating adhesion, but on the other hand, if it is too much, it is sufficient to conduct as a wire of a wire harness. It becomes difficult to secure sex. As a result of various studies, it is necessary that the total area ratio of the segmented Fe—Al-based alloy phase in the molten Al plating layer be 40% or less. The lower limit is not particularly limited as long as the Al plating adhesion amount satisfies the requirement (2), but it is desirable that the total area ratio is 5% or more. In addition, it is more preferable that the area in the cross section of the fragmented Fe—Al-based alloy phase is 0.012 mm 2 or more.

  When the area ratio of the molten Al plating layer (including the fragmented Fe-Al alloy phase dispersed therein) occupying the entire cross section of (2) is too small, sufficient conductivity as a wire of the wire harness is obtained. It becomes difficult to secure. As a result of various studies, it is necessary that the molten Al plating layer be present at an area ratio of 30% or more after satisfying the requirement (1).

  The amount of the fragmented Fe—Al alloy phase generated and the area ratio of the molten Al plating layer in the entire cross section vary depending on the immersion time in the molten Al plating bath. In other words, if the dipping time is increased, the amount of the fragmented Fe-Al alloy phase generated can be increased, thereby effectively preventing the unsolidified Al lifted along with the steel wire from flowing down from the surface of the steel wire. Therefore, it is advantageous in increasing the adhesion amount of the molten Al plating. However, in this case, since the line speed is inevitably lowered in order to increase the immersion time, in terms of reducing the amount of molten Al lifted from the bath accompanying the steel wire, the adhesion amount of molten Al plating is increased. Is negative. Therefore, by adjusting the immersion time according to the operating conditions of the molten Al plating, the “total area ratio of the fragmented Fe—Al-based alloy phase in the molten Al plated layer” and the (2 It is possible to control “the area ratio of the molten Al plating layer in the entire cross section”. However, in order to control to a desired plating adhesion amount with higher accuracy, it is desirable to use a known adhesion amount control means such as electromagnetic wiping while adjusting the immersion time.

In addition to the above (1) and (2), the Al plated steel wire of the present invention desirably further satisfies the following points.
(3) The Si content of the matrix portion excluding the fragmented Fe—Al-based alloy phase in the molten Al plating layer is 9% by mass or less.

  When Si is added to the molten Al plating bath, the melting point of the plating bath is lowered, which is advantageous in that the temperature of the plating bath can be lowered. When adding Si to the Al plating bath, the Si content is usually within a range of 15% by mass or less. However, Si in the Al plating layer is a factor that reduces the workability of the plating layer. Moreover, it leads also to electroconductivity fall. Therefore, when particularly high workability is required as a wire harness, it is desirable that the Si content of the matrix portion excluding the fragmented Fe-Al alloy phase in the molten Al plating layer is 9% by mass or less, It is more desirable that the amount be 6% by mass or less.

The Al-plated steel wire of the present invention needs to have sufficient conductivity as a strand of a wire harness, but until it has an extremely low electrical resistance equivalent to a Cu strand or an Al strand. Not required. The appropriate range varies depending on the wire diameter, but the inventors have found that the effect of reducing the electrical resistance by applying Al plating to the electrical resistance of the steel core wire itself (electrical resistance It has been found that the conductivity can be evaluated relatively well by an index expressing the (reduction effect). Specifically, the electrical resistance ρ 1 (Ω / m) per unit length of the Al-plated steel wire and the steel core wire constituting the Al-plated steel wire (assuming a state where no molten Al plating is applied) When the ratio ρ 1 / ρ 0 of the electrical resistance ρ 0 (Ω / m) per unit length is 0.55 or less, it is sufficiently applicable as a wire harness of a wire harness. More preferably, ρ 1 / ρ 0 is 0.30 or less.

  For the steel wire to be the core wire, for example, a mild steel wire specified in JIS G3505, an iron wire specified in G3532, a hard steel wire specified in G3506, and the like are applicable.

  Two kinds of Zn-plated steel wires having a diameter of 0.43 mm and 0.20 mm (core wire corresponding to a mild steel wire of JIS G3505) were obtained, and those having a diameter of 0.43 mm were subjected to wire drawing by drawing to obtain a diameter of 0.43 mm. A 40 mm Zn-plated steel wire was finished. That is, two types of Zn-plated steel wires having a diameter of 0.40 mm and 0.20 mm were prepared. The Zn plating layer thickness of these Zn-plated steel wires is about 7 μm for a 0.40 mm diameter wire and about 4 μm for a 0.20 mm diameter wire.

  The drawn Zn-plated steel wire was immersed in a molten Al plating bath without being pretreated as it was, and then subjected to molten Al plating by a method of pulling it up vertically. The composition of the molten Al plating bath is an Al-Si bath with various Si contents, and components other than Al and Si are inevitable impurities. The immersion time was adjusted by changing the line speed. By adjusting the immersion time and electromagnetic wiping, the “total area ratio of the fragmented Fe—Al-based alloy phase in the molten Al plating layer” in the above (1) and “the molten Al plating layer in the entire cross section” in the above (2) "Area ratio" was controlled to various values.

  About the obtained Al plated steel wire, a cross section perpendicular to the longitudinal direction was observed. Since it was confirmed that the diameter of the steel core wire (equivalent circle diameter) was almost equal to the diameter of the drawn Zn-plated steel wire (0.2 mm or 0.4 mm), here the diameter of the steel core wire ( The equivalent circle diameter) is displayed as 0.2 mm or 0.4 mm. By processing the optical microscope image of the cross section, the area of the entire cross section, the area of the molten Al plating layer (including the fragmented Fe—Al alloy phase dispersed therein), and the fragmented Fe—Al system The total area of the alloy phase was measured, and the “total area ratio of the fragmented Fe—Al-based alloy phase in the molten Al plating layer” in the above (1) and the “hot Al plating in the entire cross section” in the above (2) The area ratio of the layer (including the fragmented Fe-Al alloy phase dispersed therein) was determined.

  About the said cross section, "Si content of the matrix part except the fragmentary Fe-Al type alloy phase in a molten Al plating layer" of said (3) was measured by EDX.

  The amount of Al plating adhesion is a melting method for an Al plating layer (including a fragmented Fe—Al alloy phase and a continuous Fe—Al alloy layer dispersed therein) of an Al plated steel wire having a length of 1 m. Measured with

The electrical resistance ρ 0 (Ω / m) per unit length of the Zn-plated steel wire to be subjected to the molten Al plating previously measured before the molten Al plating, and the unit length of the obtained Al-plated steel wire The value of ρ 1 / ρ 0 was determined from the measured value of electrical resistance ρ 1 (Ω / m). The electrical resistance was measured at room temperature by a four-terminal method with a measurement length of 100 mm and a measurement current of 100 mA. Here, the value of ρ 0 was 0.97 Ω / m for a diameter of 0.40 mm and 3.88 Ω / m for a diameter of 0.20 mm.
A value of ρ 1 / ρ 0 that is an index of the electric resistance reduction effect is 0.3 (very good), a value of 0.30 to 0.55 is good (good), 0.55 Those exceeding □ were evaluated as x (defect), and those rated as “good” or higher were considered acceptable.

Each Al-plated steel wire was subjected to a 90 ° bending test using a 90 ° bending jig with a tip of R = 1 mm, and no crack was observed in the Al plating layer of each bending part. X (defect) was evaluated, and ○ evaluation was determined to be acceptable.
The results are shown in Tables 1 and 2.

  As can be seen from Table 1, the examples of the present invention have the above-mentioned (1) “total area ratio of fragmented Fe—Al-based alloy phases in the molten Al plating layer” and “2 By controlling the “area ratio of the molten Al plating layer to be occupied” within a specified range, the electrical resistance reduction effect was excellent. In addition, the inventive examples of Nos. 1 to 24 have a sufficiently low “Si content in the matrix portion excluding the fragmented Fe—Al-based alloy phase in the molten Al plating layer” in (3), so that bending workability is improved. The durability at the “caulking part” of the wire harness is even better.

  On the other hand, as can be seen from Table 2, in Comparative Examples No. 51 to 57, the “total area ratio of the fragmented Fe—Al-based alloy phase in the molten Al plating layer” in (1) is too large. Or, since the “area ratio of the molten Al plating layer in the entire cross section” in (2) is insufficient, the electrical resistance reduction effect is inferior.

The figure which showed typically the structure of the cross section perpendicular | vertical to the longitudinal direction in the Al plating steel wire of this invention.

Claims (5)

  1. An Al plated steel wire having a molten Al plated layer on a surface of a steel core wire having a diameter (equivalent circle diameter) of 0.1 to 0.5 mm with an Fe-Al alloy layer interposed therebetween, wherein the molten Al plated The layer is formed by immersing in a molten Al plating bath having a Si content of 0 to 15% by mass, and in a cross section perpendicular to the longitudinal direction,
    (1) The segmented Fe-Al alloy phase is dispersed in the molten Al plating layer, and the total area ratio of the segmented Fe-Al alloy phase in the molten Al plating layer is 40% or less. ,
    (2) The area ratio of the molten Al plating layer occupying the entire cross section (including the fragmented Fe-Al alloy phase dispersed therein) is 30% or more.
    Al plated steel wire.
  2. further,
    (3) The Si content of the matrix portion excluding the fragmentary Fe-Al alloy phase in the molten Al plating layer is 9% by mass or less.
    The Al plated steel wire according to claim 1.
  3. The electrical resistance ρ 1 (Ω / m) per unit length of the Al-plated steel wire and the unit length of the steel core wire constituting the Al-plated steel wire (assuming a state where molten Al plating is not applied) 3. The Al-plated steel wire according to claim 1 , wherein the ratio ρ 1 / ρ 0 of the per electric resistance ρ 0 (Ω / m) is 0.55 or less.
  4. A method for producing an Al-plated steel wire by continuously immersing a Zn-plated steel wire in a molten Al plating bath having a Si content of 0 to 15% by mass, and adjusting the immersion time in the Al plating bath (1) “total area ratio of fragmented Fe—Al alloy phase in the molten Al plating layer” and (2) “area ratio of the molten Al plating layer in the entire cross section” The manufacturing method of the Al plating steel wire in any one of Claims 1-3 controlled.
  5.   The method for producing an Al-plated steel wire according to claim 4, wherein the Zn-plated steel wire is obtained by subjecting a steel element wire to Zn plating and then drawing.
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JP5467789B2 (en) * 2009-03-31 2014-04-09 日新製鋼株式会社 Al-plated steel wire having good wire drawing workability and manufacturing method thereof
JP5464884B2 (en) * 2009-03-31 2014-04-09 日新製鋼株式会社 Al-plated steel wire excellent in wire drawing workability and manufacturing method thereof
JP5523051B2 (en) * 2009-10-19 2014-06-18 日新製鋼株式会社 Manufacturing method of hot-dip aluminum plated steel wire
JP5641756B2 (en) * 2010-03-30 2014-12-17 日新製鋼株式会社 Production method of Al plated steel wire
JP5606192B2 (en) * 2010-07-09 2014-10-15 日新製鋼株式会社 Wire bonding structure using Al plated steel wire
JP6198220B2 (en) * 2013-03-22 2017-09-20 日新製鋼株式会社 Hot-dip Al-plated steel wire, stranded wire and method for producing the same
JP6324164B2 (en) * 2013-12-17 2018-05-16 日新製鋼株式会社 Composite stranded wire
MX2016017044A (en) 2014-07-03 2017-05-12 Nisshin Steel Co Ltd MOLTEN Al PLATED STEEL WIRE AS WELL AS STRANDED WIRE AND MANUFACTURING METHOD THEREFOR.

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JPH06299312A (en) * 1993-04-15 1994-10-25 Kobe Steel Ltd Surface-treated steel material excellent in corrosion resistance and its production
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JP4653389B2 (en) * 2003-06-05 2011-03-16 新日本製鐵株式会社 High-strength Al-plated wire rod and bolt excellent in delayed fracture resistance, and method for producing the same
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