JP4374356B2 - High-strength wire rod excellent in wire drawing characteristics, manufacturing method thereof, and high-strength steel wire excellent in wire drawing properties - Google Patents

Description

  The present invention relates to a high-strength wire having excellent wire drawing characteristics used for drawing to a PC steel wire, galvanized steel stranded wire, spring steel wire, suspension bridge cable, etc., a method for producing the same, and wire drawing properties It relates to high-strength steel wires with excellent resistance.

  When producing high carbon hard steel wire, it is usually necessary to perform a patenting treatment on the hot-rolled wire, and then draw it into a steel wire with a predetermined wire diameter. Such treatment ensures a strength of 1600 MPa or more. At the same time, it is required to ensure sufficient performance with respect to toughness evaluated by the fracture drawing value.

In response to the above-described requirements, attempts have been made to improve the drawing workability of high carbon wire by controlling segregation and microstructure or by containing specific elements.
The drawing value of the patenting wire depends on the austenite particle size, and the drawing value is improved by making the austenite particle size finer. Therefore, by using carbides and nitrides such as Nb, Ti, and B as pinning particles, austenite is obtained. Attempts have also been made to reduce the particle size.

  The group consisting of Nb: 0.01 to 0.1% by weight, Zr: 0.05 to 0.1% by weight, Mo: 0.02 to 0.5% by weight as component elements in the high carbon wire Has proposed a wire rod containing at least one kind (see, for example, Patent Document 1).

Moreover, the wire which refine | miniaturized the austenite particle size by making NbC contain in a high carbon wire is proposed (for example, refer patent document 2).
Japanese Patent No. 2609387 JP 2001-131697 A

  The wire described in Patent Document 1 has a component composition in which the ductility of the steel wire is increased by including the above-described component elements. However, in the wire described in Patent Document 1, since the component elements to be added are all expensive, the manufacturing cost may increase.

  In the wire described in Patent Document 2, the wire drawing workability is improved by using NbC as pinning particles. However, in the wire described in Patent Document 2, since the contained component elements are all expensive, the manufacturing cost may increase. In addition, Nb forms coarse carbides and nitrides, and Ti forms coarse oxides, so that these become starting points for destruction, and there is a possibility that the wire drawing property is lowered.

  By the way, it has been confirmed that increasing the amount of C and the amount of Si in the steel material component is the most economical and effective means for increasing the strength of the high carbon steel wire. However, since the precipitation of ferrite is promoted with the increase of Si and the precipitation of cementite is suppressed, even when the hypereutectoid composition is such that the C content exceeds 0.8%, the patenting process is performed. When cooling from the austenite region, proeutectoid ferrite tends to precipitate in a plate shape along the austenite grain boundary.

  Furthermore, since the eutectoid temperature of pearlite is increased by the addition of Si, a supercooled structure such as pseudo pearlite or bainite tends to be generated in a temperature range of 480 to 650 ° C. where normal patenting is performed. As a result, the fracture drawing value of the wire after the patenting treatment is reduced, the ductility is deteriorated, and the frequency of disconnection during the wire drawing process is increased, leading to a reduction in productivity and yield.

  Therefore, the present invention has been made in view of the above circumstances, and has a low-cost configuration, a high yield, a high aperture value, a high-strength wire excellent in wire drawing characteristics, a manufacturing method thereof, and wire drawing characteristics. The object is to provide an excellent high-strength steel wire.

  As a result of intensive studies to achieve the above object, the present inventors have made solid solution B in an amount corresponding to the amount of C and Si present in the austenite before the patenting treatment, thereby allowing cementite precipitation and ferrite. We have found that high carbon pearlite wire with a high non-perlite structure and high drawing value can be obtained by balancing the driving force of precipitation, and that it is possible to achieve both workability and high strength due to excellent wire drawing characteristics. It came to do.

That is, the gist of the present invention is as follows.
[1] By mass%
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.006%,
Al: 0.005 to 0.1% is contained,
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
The area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundaries in the depth part from the surface layer to 100 μm is 10% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics.
[2] In mass%,
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.006%,
Al: 0.005 to 0.1% is contained,
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
Within the cross section from the surface layer of the wire rod to the center, the area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary is 5% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics.
[3] Further, in mass%, Cr: 0.5% or less (not including 0%), Ni: 0.5% or less (not including 0%), Co: 0.5% or less (0% V: 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%), Mo: 0.2% or less (not including 0%), W : At least one selected from the group consisting of: 0.2% or less (not including 0%), Nb: 0.1% or less (not including 0%) [1] Or the high intensity | strength wire excellent in the wire drawing characteristic as described in [2].
[4] By mass%,
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.006%,
Ti: 0.005 to 0.1%,
Al: containing 0.1% or less,
Further, Cr: 0.5% or less (not including 0%), Ni: 0.5% or less (not including 0%), Co: 0.5% or less (not including 0%), V: 0 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%), Mo: 0.2% or less (not including 0%), W: 0.2% or less ( 0% not included), Nb: containing at least one selected from the group consisting of 0.1% or less (not including 0%),
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
The area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary in the depth part from the surface layer to 100 μm is 10% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics.
[5] In mass%,
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.005%,
Ti: 0.005 to 0.1%,
Al: containing 0.1% or less,
Further, Cr: 0.5% or less (not including 0%), Ni: 0.5% or less (not including 0%), Co: 0.5% or less (not including 0%), V: 0 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%), Mo: 0.2% or less (not including 0%), W: 0.2% or less ( 0% not included), Nb: containing at least one selected from the group consisting of 0.1% or less (not including 0%),
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
Within the cross section from the surface layer of the wire rod to the center, the area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary is 5% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics.
[6] A steel slab having the chemical composition according to any one of [1] to [5] is hot-rolled, wound at a temperature of Tr = 800 to 950 ° C., and then hot-rolled. Within the time t1 shown by the following formula (2) after the subsequent cooling / winding step, it is once immersed in a molten salt of 480-650 ° C., or once at 200 ° C. by means of molten salt, stealmore or air cooling. A method for producing a high-strength wire rod excellent in wire drawing characteristics, characterized in that after cooling to below, re-austenitizing at 950 ° C. or higher, and then patented by immersing in molten lead at 480-650 ° C. .
t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ((N−Ti / 3.41) × 0.71−B + 0.0003) (2)
However, when ((N−Ti / 3.41) × 0.71−B + 0.0003) is 0 or less, or when t1 is greater than 40 s, t1 = 40 s.
[7] A steel slab having the chemical composition according to any one of [1] to [5] is cooled immediately after hot rolling and wound at a temperature of 800 to 950 ° C., and then after hot rolling. Cooling to the temperature range of 480 to 650 ° C. at the cooling rate in the range of 15 to 150 ° C./sec within the time t1 shown by the formula (2) after the cooling and winding process, and patenting treatment in this temperature range The manufacturing method of the high strength wire rod excellent in the wire drawing characteristic characterized by this.
[8] High-strength steel manufactured by cold-drawing the wire manufactured by the method according to [6] or [7] from the steel according to any one of [1] to [5] The tensile strength TS is 1600 MPa or more, the area ratio of the non-pearlite structure is 10% or less, and the balance is a pearlite structure at a depth of 50 μm from the surface layer. High strength steel wire.
[9] High-strength steel produced by cold-drawing the wire produced by the method according to [6] or [7] from the steel according to any one of [1] to [5] It is a wire, the tensile strength TS is 1600 MPa or more, the area ratio of the non-pearlite structure is 5% or less in the cross section from the surface of the wire to the center, and the remainder is a pearlite structure High strength steel wire.

According to the high-strength wire rod excellent in drawability of the present invention, C: 0.7-1.2%, Si: 0.35-1.5%, Mn: 0.1-1.0 in mass%. %, N: 0.001 to 0.006%, Al: 0.005 to 0.1%, and further containing B in a range given by 0.0004 to 0.0060%, and solid solution The amount of B is 0.0002% or more, the balance is made of Fe and inevitable impurities, and the tensile strength TS [MPa] is expressed by the formula {TS> (1000 × C [%] − 10 × wire diameter [mm] +450)} The area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary at a depth of 100 μm from the surface layer is 10% or less, or the wire surface layer Area of non-pearlite structure in the cross section from the center There are 5% or less, it has a configuration in which the balance of pearlite structure.
With the relationship of the composition of each component as described above, the solid solution B in an amount corresponding to the amount of C and Si is present in the austenite before the patenting treatment, thereby balancing the driving force of cementite precipitation and ferrite precipitation. By suppressing the generation of the structure, ductility is improved and disconnection in wire drawing can be prevented, and productivity and yield are improved.
In addition, a steel wire having a structure mainly composed of pearlite and having a reduced area ratio of a non-pearlite structure can be obtained, as a PC steel wire, a galvanized steel wire, a spring steel wire, a cable for a suspension bridge Can improve performance.

Hereinafter, embodiments of a high-strength wire rod excellent in wire drawing characteristics and a manufacturing method thereof and a high-strength steel wire excellent in wire drawing properties according to the present invention will be described with reference to the drawings.
Note that this embodiment is described in detail for better understanding of the gist of the invention, and thus does not limit the present invention unless otherwise specified.

[High-strength wire]
The high-strength steel wire having excellent wire drawing characteristics according to the present embodiment is mass%, C: 0.7 to 1.2%, Si: 0.35 to 1.5%, Mn: 0.1 to 1. 0%, N: 0.001 to 0.006%, Al: 0.005 to 0.1%, and B in a range given by 0.0004 to 0.0060%. The amount of dissolved B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
The area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundaries in the depth portion from the surface layer to 100 μm is 10% or less, or from the wire surface layer to the center portion The area ratio of the non-pearlite structure in the cross section is 5% or less, and the remainder is a pearlite structure.

  Further, in the high-strength wire rod having excellent wire drawing characteristics according to the present embodiment, B is 0 when Ti is contained in the range of 0.005 to 0.1% by mass instead of Al of the above-described components. .Components that are contained within the range given by 0004 to 0.0060% and that the amount of solute B is 0.0002% or more, and further contain Al in 0.1% or less. Can do.

  Further, in the high-strength wire rod having excellent wire drawing characteristics according to the present embodiment, in addition to the above-described components, by mass%, Cr: 0.5% or less (excluding 0%), Ni: 0.5% or less ( Co: 0.5% or less (not including 0%), V: 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%) ), Mo: 0.2% or less (not including 0%), W: 0.2% or less (not including 0%), Nb: 0.1% or less (not including 0%) It can be set as the structure containing at least 1 or more types selected.

  In this embodiment, the component composition of the wire is limited for reasons described later, and the pearlite transformation is performed by limiting the winding temperature during rolling, the time from winding to patenting, and the cooling rate during the patenting process. It suppresses the precipitation of non-pearlite structure at the time, and is a wire material excellent in strength characteristics and wire drawing characteristics.

(Component composition)
Below, the reason for limitation of each component composition of the high intensity | strength wire rod excellent in the wire drawing characteristic of this embodiment is demonstrated.
(C: 0.7-1.2%)
C is an element effective for increasing the strength of the wire. When the C content is less than 0.7%, it is difficult to stably give the final product the high strength specified in the above formula (1), and at the same time, precipitation of pro-eutectoid ferrite at the austenite grain boundaries. Is promoted, and it becomes difficult to obtain a uniform pearlite structure. On the other hand, if the content of C is too large, not only is the net-form pro-eutectoid cementite generated at the austenite grain boundaries and breakage is likely to occur during wire drawing, but the toughness and ductility of the ultrafine wire after the final wire drawing is increased. Deteriorate significantly. Therefore, the C content is within a range of 0.7 to 1.2% by mass.

(Si: 0.35-1.5%)
Si is an element effective for increasing the strength. Furthermore, it is an element useful as a deoxidizer, and is also an element necessary when targeting a steel wire containing no Al. On the other hand, if the amount of Si is too large, precipitation of pro-eutectoid ferrite is promoted even in hypereutectoid steel, and the limit working degree in wire drawing decreases. Furthermore, the wire drawing process by mechanical descaling (hereinafter abbreviated as MD) becomes difficult. Therefore, the Si content is within a range of 0.35 to 1.5% by mass.

(Mn: 0.1 to 1.0%)
Mn is an element useful as a deoxidizer like Si. It is also effective in improving the hardenability and increasing the strength of the wire. Furthermore, Mn has the effect | action which fixes S in steel as MnS and prevents hot brittleness. If the content is less than 0.1% by mass, it is difficult to obtain the above effect. On the other hand, Mn is an element that easily segregates, and when it exceeds 1.0 mass%, segregation occurs particularly in the center of the wire, and martensite and bainite are generated in the segregated portion, so that the wire drawing workability decreases. Therefore, the content of Mn is set within a range of 0.1 to 1.0% by mass.

(Al: 0.005 to 0.1%)
Al is effective as a deoxidizing material. Moreover, it has the effect of fixing N and suppressing aging and increasing the solid solution B. The Al content is preferably in the range of 0.005 to 0.1%. If the Al content is less than 0.005%, it is difficult to obtain an effect of fixing N. If the Al content exceeds 0.1%, a large amount of hard non-deformation alumina-based nonmetallic inclusions are generated, and the ductility and wire drawing of the steel wire are lowered. In addition, when Ti described later is added, the above effect can be obtained without adding Al by fixing Ti to Ti, so there is no need to define the lower limit of Al, and the content of Al is 0 may be sufficient.

(Ti: 0.005 to 0.1%)
Ti is effective as a deoxidizer. Moreover, it precipitates as TiN, contributes to preventing the coarsening of the austenite grain size, and is an effective element effective for securing the amount of dissolved B in the austenite by fixing N. When the Ti content is less than 0.005%, the above-described effects are hardly obtained. If the Ti content exceeds 0.1%, coarse carbides are formed in austenite, and the drawability may be reduced. Therefore, the Ti content is within the range of 0.005 to 0.1% by mass.

(N: 0.001 to 0.006%)
N produces Al, B or Ti and nitride in steel and has the effect of preventing coarsening of the austenite grain size during heating, and the effect is effectively exhibited by containing 0.001% or more. . However, if the content becomes too large, the amount of nitride increases too much, and the amount of dissolved B in austenite is reduced. Further, solute N may promote aging during wire drawing. Therefore, the N content is set in a range of 0.001 to 0.006% by mass%.

(B: 0.0004 to 0.0060%)
When B is present in austenite in a solid solution state, B has an effect of concentrating at the grain boundary to suppress precipitation of pro-eutectoid ferrite and promote precipitation of pro-eutectoid cementite. Therefore, it is possible to suppress the formation of pro-eutectoid ferrite by adding an appropriate amount according to the balance between the amounts of C and Si. Since B forms a nitride, it is necessary to consider the balance with the N amount in addition to C and Si in order to secure the B amount in a solid solution state. On the other hand, when B is added too much, not only the precipitation of pro-eutectoid cementite is promoted, but also coarse Fe ₃ (CB) ₆ carbides are formed in austenite, which may reduce the drawability. About these relationships, the present inventors repeated experiments and set it as 0.0004 to 0.0060% as the optimum range of the B content. In addition, B needs to exist in a solid solution state before a patenting process, and needs to be 0.0002% or more as a solid solution B amount in the wire after rolling.

  The impurities P and S are not particularly defined, but are each preferably 0.02% or less from the viewpoint of ensuring ductility as in the case of conventional ultra fine steel wires.

  The high-strength steel wire rod described in the present embodiment has the above-mentioned components as a basic composition, but for the purpose of further improving mechanical properties such as strength, toughness, ductility, etc., the selective tolerance described below It is good also as a component composition which contained the additive element 1 type, or 2 or more types positively.

(Cr: 0.5% or less)
Cr is an element effective for reducing the lamella spacing of pearlite and improving the strength of the wire and the wire drawing workability. Addition of 0.1% or more is preferable for effectively exhibiting such an action. On the other hand, if the amount of Cr is too large, the transformation end time becomes long, and there is a possibility that a supercooled structure such as martensite and bainite is formed in the hot-rolled wire, and the mechanical descaling property is also deteriorated. 0.5%.

(Ni: 0.5% or less)
Ni is an element that does not contribute much to increasing the strength of the wire, but increases the toughness of the wire. Addition of 0.1% or more is preferable for effectively exhibiting such an action. On the other hand, if Ni is added excessively, the transformation end time becomes longer, so the upper limit was made 0.5%.

(Co: 0.5% or less)
Co is an element effective for suppressing precipitation of pro-eutectoid cementite in the rolled material. Addition of 0.1% or more is preferable for effectively exhibiting such an action. On the other hand, even if Co is added excessively, the effect is saturated and the excess content is wasted, and the manufacturing cost may increase, so the upper limit was set to 0.5%.

(V: 0.5% or less)
V forms fine carbonitrides in the ferrite, thereby preventing austenite grains from coarsening during heating and contributing to an increase in strength after rolling. Addition of 0.05% or more is preferable for effectively exhibiting such an action. However, if the amount is excessively added, the amount of carbonitride formed becomes too large and the particle size of the carbonitride increases, so the upper limit was made 0.5%.

(Cu: 0.2% or less)
Cu has the effect of increasing the corrosion resistance of the ultrafine steel wire. Addition of 0.1% or more is preferable for effectively exhibiting such an action. However, if added excessively, it reacts with S and segregates CuS in the grain boundaries, so that flaws are generated in the steel ingot, wire, etc. during the wire manufacturing process. In order to prevent such adverse effects, the upper limit was made 0.2%.

(Mo: 0.2% or less)
Mo has the effect of increasing the corrosion resistance of the ultrafine steel wire. Addition of 0.1% or more is preferable for effectively exhibiting such an action. On the other hand, if Mo is added excessively, the transformation end time becomes long, so the upper limit was made 0.2%.

(W: 0.2% or less)
W has the effect of increasing the corrosion resistance of the ultrafine steel wire. Addition of 0.1% or more is preferable for effectively exhibiting such an action. On the other hand, if W is added excessively, the transformation end time becomes longer, so the upper limit was made 0.2%.

(Nb: 0.1% or less)
Nb has the effect of increasing the corrosion resistance of the ultrafine steel wire. Addition of 0.05% or more is preferable for effectively exhibiting such an action. On the other hand, if Nb is added excessively, the transformation end time becomes longer, so the upper limit was made 0.1%.

(Structure of wire rod)
According to various studies conducted by the present inventors, the wire drawing workability of the wire is particularly affected mainly by bainite precipitated at the prior austenite grain boundaries of the wire, in addition to proeutectoid ferrite, pseudo It is clear that it is non-perlite composed of pearlite. Therefore, like the wire rod of this embodiment, in the portion from the surface layer to a depth of 100 μm, the area ratio of the non-pearlite structure is 10% or less, thereby improving the wire drawing workability and generating delamination. It was confirmed that it could be suppressed.

  In the present embodiment, by using wire rod steel that satisfies the requirements of the above component composition, it is hot-rolled and then directly patented, or it is re-austenitized after rolling and cooling and then patented. In addition, it is possible to obtain a wire material in which the main structure is made of pearlite and the area ratio of the non-pearlite structure is 10% or less at a depth of 100 μm from the surface layer. (See, for example, FIG. 1. FIG. 1 is an SEM photograph showing the structure of the patenting material. In FIG. 1, the black part is a non-pearlite structure made of bainite, ferrite, etc., and the white part is a pearlite structure.)

  On the other hand, the disconnection at the time of wire drawing is often due to the coupling disconnection due to the defective structure in the center of the wire, reducing the non-pearlite structure in the center of the wire and improving the aperture value after patenting to reduce the disconnection rate It is valid. As in the wire of the present embodiment, it was confirmed that the aperture value was improved by setting the area ratio of the non-pearlite structure to 5% or less in the cross section from the surface of the wire to the center.

[Method for producing high-strength wire]
In order to obtain a wire having the structure and tensile strength defined in the present embodiment by using the steel having the component composition defined in the present embodiment, during the conveyance from winding after rolling to patenting treatment, B It is necessary not to form carbides or nitrides and to cool at a rate higher than a certain value during the patenting process. According to the study by the present inventors, after heating to 1050 ° C., rapidly cooling to a temperature of 750 to 950 ° C. within 1 second, and subsequently holding at this temperature for a certain period of time, the lead-patented wire structure and solute B As a result of measuring the amount, the holding time of the limit containing 0.0002% or more of the solid solution B becomes a C curve determined by the combination of the B amount and the N amount as shown in FIG. ).
t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ( ( N−Ti / 3.41 ) × 0.71− B + 0.0003) (2)

In the formula (2), Tr is a winding temperature, and ( ( N−Ti / 3.41 ) × 0.71− B + 0.0003) is effective in a component range larger than 0 (zero). If it is (zero) or less, there is no limit on the holding time. In actual rolling, it hardly takes 40 seconds or more after winding up to start the patenting process, and the upper limit is 40 seconds.

  Based on the above, the wire rolled at 1050 ° C. or higher is water-cooled, wound at a temperature of 800 ° C. or higher, preferably 850 ° C. or higher and 950 ° C. or lower, and the time from winding to the start of patenting treatment is It is necessary to make it within the formula (2). When the temperature at the time of winding is less than 800 ° C., B precipitates as a carbide and the effect of suppressing the non-pearlite structure as solid solution B becomes insufficient. When the temperature at the time of winding exceeds 950 ° C., the γ particle size becomes coarse and the aperture value decreases.

  After winding the wire, a patenting process is then performed. The patenting treatment of the wire may be performed by directly immersing in molten salt or molten lead at a temperature of 480 to 650 ° C., or once cooled and heated to 950 ° C. or higher to re-austenite, and then 480 to 650. And a cooling rate of 15 to 150 ° C./sec (where the cooling rate is from 700 ° C. until the recuperation associated with the transformation starts) Before and after), which means that cooling is performed by the cooling method after that.) Is cooled to a temperature range of 480 to 650 ° C., and patenting is performed in this temperature range. Can be adopted.

By this patenting treatment, it is possible to suppress the non-pearlite structure in the cross section of the wire to 5% or less and to secure a tensile strength TS that is greater than that represented by the above formula (1).
In addition to this, in order to suppress overcooling and suppress the area ratio of the non-pearlite structure to 10% or less at a depth of 100 μm from the surface layer, the temperature of the molten salt or molten lead is set to 520 ° C. or higher. It is desirable.
In addition, in this embodiment, the outstanding wire drawing characteristic and high intensity | strength can be stably obtained by making the diameter of a wire into the range of 5.5-18 mm.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and is implemented with appropriate modifications within a scope that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

<Sample preparation method>
The test steel of each component shown in Table 1 and Table 3 was made into a slab having a cross-sectional size of 300 × 500 mm by a continuous casting facility, and a steel slab having a 122 mm square cross section was produced by split rolling. Thereafter, it is rolled into a wire having a predetermined diameter under the conditions shown in Table 2 and Table 4, wound at a predetermined temperature, and directly molten salt patenting (DLP) or reheated molten lead patenting ( LP) Cooling was performed, and No. 1-15 and no. Nos. 31 to 43 and Nos. 16-30 and no. Each sample shown to 44-55 was obtained. These sample Nos. The following evaluation tests were conducted for 1 to 55.

<Evaluation test method>
The solid solution B was obtained by measuring the amount of B present as a compound in the electrolytic extraction residue of the patenting wire by the curcumin spectrophotometry and determining the difference from the total amount of B.
Regarding the non-pearlite structure fraction, the patenting wire and the drawn wire were embedded and polished, and after chemical corrosion using picric acid, the non-perlite structure fraction was measured by SEM observation in the cross section (L cross section) parallel to the length direction of the wire. Perlite organization rate was determined.
As for the non-pearlite structure ratio of the rolled wire rod, an L cross section appears by cutting and polishing at a portion ± 5% of the radius from the center of the wire rod, and the depth of the surface layer portion is 100 μm × width at a magnification of 2000 by SEM observation A tissue photograph of a 100 μm region was taken for each of five visual fields, and the average value of the area ratio was measured by image analysis.
Regarding the non-pearlite structure ratio of the drawn steel wire, an L cross-section appears by cutting and polishing at a portion ± 5% of the radius from the center of the wire, and the surface layer portion is deepened at a magnification of 2000 times by SEM observation. A tissue photograph of a region having a thickness of 40 μm × width of 100 μm was taken for each five views, and an average value of the area ratio was measured by image analysis.
From this measurement, it was confirmed that the non-pearlite structure area ratio before wire drawing and the non-pearlite structure area ratio after wire drawing almost coincided.
In addition, when the decarburization layer existed in the surface layer, all the decarburization parts prescribed | regulated by 4 of JISG0558 were excluded from the measurement site | part.
Regarding the tensile strength TS, the gauge length was 200 mm, a tensile test was performed at a speed of 10 mm / min, and an average value of n = 3 was measured.

  Hereinafter, No. in Table 1 1-15 and no. Table 2 shows a list of evaluation test conditions and results for each sample shown in 31-43.

  In Tables 1 and 2, no. Each sample shown in 1 to 15 is a high-strength wire (invented steel) having excellent wire drawing characteristics according to the present invention. Each sample shown to 31-43 is the conventional wire (comparison steel).

As shown in Table 2, no. The wires of the samples (present invention steels) shown in 1 to 15 all satisfy the range in which the B content is given by 0.0004 to 0.0060%, and the time until the start of patenting after winding is t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ( ( N−Ti / 3.41 ) × 0.71− B + 0.0003) or less is satisfied. For this reason, the amount of solute B in each case was 0.0002% or more, and the non-pearlite structure area ratio in the cross section from the surface of the wire rod to the center was 5% or less. In addition, the strength of any patenting material exceeds the strength (TS threshold value) represented by TS = (1000 × C [%] − 10 × wire diameter [mm] +450).

  In addition, No. Only the sample No. 11 (steel of the present invention) had a salt temperature of 505 ° C., which was lower than that of the present invention, but the non-pearlite area ratio of the wire surface layer exceeded 10%. Delamination has occurred. On the other hand, no. Since the steels of the present invention other than the 11 samples have a lead or salt temperature of 520 ° C. or higher, the non-pearlite area ratio of the wire surface layer is suppressed to 10% or less.

In contrast, no. In the wire rod of the sample (comparative steel) shown in No. 31, since the winding temperature was as low as 750 ° C., B carbide precipitated before the patenting treatment, and the non-pearlite structure could not be suppressed.
No. In the sample (comparative steel) wires shown in Nos. 32 and 37, the time from winding to the start of patenting is t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ( ( N Since it was longer than -Ti / 3.41 ) × 0.71 -B + 0.0003), solid solution B could not be secured, and the non-pearlite structure could not be suppressed.
No. In the wire rod of the sample (comparative steel) shown in Fig. 38, the molten lead temperature at the time of patenting was 450 ° C, which was lower than the specified value, so that the occurrence of a non-pearlite structure could not be suppressed.
No. In the wires of the samples (comparative steels) shown in 33 and 41, the B content was more than the predetermined amount, and B carbide and proeutectoid cementite were precipitated.
No. In the sample (comparative steel) shown in No. 34, since the Si content was excessive at 1.6%, generation of a non-pearlite structure could not be suppressed.
No. In the wire of the sample (comparative steel) shown in 35, since the C content was excessive as 1.3%, it was not possible to suppress the precipitation of proeutectoid cementite.
No. In the wire of the sample (comparative steel) shown in 36, since the Mn content is excessive at 1.5%, the generation of micromartensite could not be suppressed.
No. In the wire samples of 39 and 40 (comparative steel), the cooling speed during the patenting process was smaller than the specified cooling speed, so that the tensile strength with the specified LP material and the tensile strength after wire drawing can be satisfied. There wasn't.
No. In the wires of the samples (comparative steel) shown in 42 and 43, the B content was less than the prescribed amount, so the formation of a non-pearlite structure could not be suppressed and was 5% or more.

  Next, No. in Table 3 16-30 and no. Table 4 shows a list of evaluation test conditions and results for the samples shown in 44 to 55.

  In Tables 3 and 4, no. Each sample shown to 16-30 is the high intensity | strength wire rod (this invention steel) excellent in the wire drawing characteristic which concerns on this invention, and No.1. Each sample shown to 44-55 is a conventional wire (comparison steel).

As shown in Table 4, no. The wires of the samples (invention steels) shown in 16 to 30 satisfy the range where the B content is given by 0.0004 to 0.0060%, and the time until the start of patenting after winding is t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ( ( N−Ti / 3.41 ) × 0.71− B + 0.0003) or less is satisfied. For this reason, the amount of solute B in each case was 0.0002% or more, and the non-pearlite structure area ratio in the cross section from the surface of the wire rod to the center was 5% or less. In addition, the strength of any patenting material exceeds the strength (TS threshold value) represented by TS = (1000 × C [%] − 10 × wire diameter [mm] +450).

  In addition, No. Only sample 27 (steel of the present invention) had a salt temperature of 490 ° C., which was lower than that of the present invention, but the non-pearlite area ratio of the wire surface layer exceeded 10%. Delamination has occurred. On the other hand, no. Since the steels of the present invention other than the sample No. 27 have a lead or salt temperature of 520 ° C. or more, the non-pearlite area ratio of the wire surface layer is suppressed to 10% or less.

In contrast, no. In the wire of the sample (comparative steel) shown in No. 44, since the coiling temperature was as low as 750 ° C., B carbide precipitated before the patenting treatment, and the non-pearlite structure could not be suppressed.
No. In the sample (comparative steel) wires shown in 50, 52, 53, and 54, the time from winding up to the start of patenting is t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ((N-Ti / 3.41 ) × 0.71 -B + 0.0003) for longer than can not be ensured solid solution B, it was not able to suppress the non-pearlite structures.
No. In the wire of the sample (comparative steel) shown in FIG. 49, the molten lead temperature at the time of patenting was 450 ° C., which was lower than the specified value, and therefore the generation of a non-pearlite structure could not be suppressed.
No. In the wire rod of the sample (comparative steel) shown in 45, the B content was more than a predetermined amount, and B carbide and pro-eutectoid cementite were precipitated.
No. In the wire of the sample (comparative steel) shown in No. 46, since the Si content was excessive at 1.6%, generation of a non-pearlite structure could not be suppressed.
No. In the sample (comparative steel) wire shown in 47, the content of Mn was excessive at 1.6%, and therefore the formation of micromartensite could not be suppressed.
No. In the wire rods of the samples (comparative steel) shown in 48, 51, and 55, the B content was less than the prescribed amount, so the generation of a non-pearlite structure could not be suppressed, and it was 5% or more.

  In addition, No. A steel wire for PWS with a diameter of φ5.2 mm was manufactured using 19, 21, 26 (steel of the present invention), and a steel wire having a tensile strength TS of 2069 MPa, 2060 MPa, and 2040 MPa, respectively, and causing no delamination was obtained. We were able to make it. On the other hand, no. When a similar prototype was made using a wire of No. 27 (steel of the present invention), the tensile strength TS was 1897 MPa and delamination did not occur, but the number of twists for fracture was No. Compared to the cases of 19, 21, 26, it was reduced by about 30%. On the other hand, no. When a similar trial production was carried out using a wire of 52 (comparative steel), delamination occurred with a tensile strength TS of 1830 MPa.

FIG. 3 is a graph showing the relationship between the wire diameter of the wire after the patenting treatment and the area ratio of the non-pearlite structure in the cross section from the surface of the wire to the center. Note that in FIG. Samples 1 to 15 (steel of the present invention) are shown. Each sample (comparative steel) of 31-43 is shown. In addition, ● indicates no. Samples 16 to 30 (present invention steel) are shown. Each sample (comparative steel) of 44-55 is shown.
From the graph shown in FIG. 3, the high-strength wire rod (◆, ●) according to the present invention has a non-pearlite area ratio of 5% or less stably regardless of the wire diameter, whereas the conventional wire rod of the comparative example ( In (◇, ○), the area ratio of the non-pearlite structure is a value exceeding 5%.

FIG. 4 is a graph showing the relationship between the tensile strength TS and the drawing value of the wire after the patenting process. Note that in FIG. Samples 1 to 15 (steel of the present invention) are shown. Each sample (comparative steel) of 31-43 is shown. In addition, ● indicates no. Samples 16 to 30 (present invention steel) are shown. Each sample (comparative steel) of 44-55 is shown.
From the graph shown in FIG. 4, when the tensile strength TS is the same, the aperture value of the high-strength wire (◆, ●) according to the present invention is superior to the conventional wire (◇, ○) of the comparative example. Obviously.

  As described above, in the present invention, the component composition of the steel material to be used is specified, and the amount of solid solution B corresponding to C and Si is present in the austenite before the patenting treatment, whereby cementite precipitation and ferrite A hard steel wire having a structure mainly composed of pearlite and having a non-pearlite structure area ratio of 5% or less can be obtained by balancing the driving force of precipitation, PC steel wire, galvanized steel wire, The performance as a spring steel wire, steel cord steel wire, suspension bridge cable, etc. can be improved.

FIG. 1 is an SEM photograph showing the structure of the patenting material. FIG. 2 is a graph showing BN precipitation curves when the amounts of B and N are different. FIG. 3 is a graph showing the relationship between the wire diameter and the pro-eutectoid ferrite area ratio in the wire after the patenting treatment. FIG. 4 is a graph showing the relationship between the tensile strength and the drawing value of the wire after the patenting process.

Claims (9)

% By mass
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.006%,
Al: 0.005 to 0.1% is contained,
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
The area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary in the depth part from the surface layer to 100 μm is 10% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics. % By mass
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.006%,
Al: 0.005 to 0.1% is contained,
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
Within the cross section from the surface layer of the wire rod to the center, the area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary is 5% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics. Further, in mass%, Cr: 0.5% or less (excluding 0%), Ni: 0.5% or less (not including 0%), Co: 0.5% or less (not including 0%) V: 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%), Mo: 0.2% or less (not including 0%), W: 0.0. 2% or less (not including 0%), Nb: contain at least one selected from the group consisting of 0.1% or less (not including 0%) in claim 1 or 2, characterized in High-strength wire with excellent wire drawing characteristics. % By mass
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.006%,
Ti: 0.005 to 0.1%,
Al: containing 0.1% or less,
Further, Cr: 0.5% or less (not including 0%), Ni: 0.5% or less (not including 0%), Co: 0.5% or less (not including 0%), V: 0 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%), Mo: 0.2% or less (not including 0%), W: 0.2% or less ( 0% not included), Nb: containing at least one selected from the group consisting of 0.1% or less (not including 0%),
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
The area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary in the depth part from the surface layer to 100 μm is 10% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics. % By mass
C: 0.7 to 1.2%
Si: 0.35-1.5%,
Mn: 0.1 to 1.0%,
N: 0.001 to 0.005%,
Ti: 0.005 to 0.1%,
Al: containing 0.1% or less,
Further, Cr: 0.5% or less (not including 0%), Ni: 0.5% or less (not including 0%), Co: 0.5% or less (not including 0%), V: 0 0.5% or less (not including 0%), Cu: 0.2% or less (not including 0%), Mo: 0.2% or less (not including 0%), W: 0.2% or less ( 0% not included), Nb: containing at least one selected from the group consisting of 0.1% or less (not including 0%),
Furthermore, it contains B in a range given by 0.0004 to 0.0060%, and the amount of solid solution B is 0.0002% or more, and the balance consists of Fe and inevitable impurities,
The tensile strength TS [MPa] is represented by the following formula (1):
TS> (1000 × C [%] − 10 × wire diameter [mm] +450) (1)
Within the cross section from the surface layer of the wire rod to the center, the area ratio of the non-pearlite structure consisting of proeutectoid ferrite, pseudo pearlite or bainite precipitated along the prior austenite grain boundary is 5% or less, and the remainder is the pearlite structure High strength wire rod with excellent wire drawing characteristics. The steel slab having the chemical composition according to any one of claims 1 to 5 is hot-rolled, wound at a temperature of Tr = 800 to 950 ° C, and then cooled and wound after hot-rolling. After the taking step, within a time t1 represented by the following formula (2), after being directly immersed in a molten salt of 480 to 650 ° C. or once cooled to 200 ° C. or lower by means of molten salt, stealmore or air cooling. A method for producing a high-strength wire rod excellent in wire drawing characteristics, characterized in that after re-austenitizing at 950 ° C. or higher, it is subjected to patenting treatment by immersing in molten lead at 480 ° C. to 650 ° C.
t1 = 0.0013 × (Tr−815) ² + 7 × (B−0.0003) / ((N−Ti / 3.41) × 0.71−B + 0.0003) (2)
However, when ((N−Ti / 3.41) × 0.71−B + 0.0003) is 0 or less, or when t1 is greater than 40 s, t1 = 40 s.   A steel slab having the chemical composition according to any one of claims 1 to 5 is cooled immediately after hot rolling and wound at a temperature of 800 to 950 ° C, and then cooled and wound up after hot rolling. The elongation is characterized by cooling to a temperature range of 480 to 650 ° C. at a cooling rate in the range of 15 to 150 ° C./sec within a time t 1 shown later in formula (2), and performing a patenting treatment in this temperature range. A method for producing high-strength wires with excellent wire properties.   A high-strength steel wire produced by cold-drawing a wire produced by the method of claim 6 or 7 from the steel material according to any one of claims 1 to 5, wherein the tensile strength is high A high-strength steel wire having a thickness TS of 1600 MPa or more, an area ratio of a non-pearlite structure of 10% or less at a depth of 50 μm from the surface layer, and the balance being a pearlite structure.   A high-strength steel wire produced by cold-drawing a wire produced by the method of claim 6 or 7 from the steel material according to any one of claims 1 to 5, wherein the tensile strength is high A high-strength steel wire having a thickness TS of 1600 MPa or more, an area ratio of a non-pearlite structure of 5% or less, and the remainder being a pearlite structure in a cross section from the surface of the wire to the center.

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