WO2015115574A1 - 疲労特性に優れたばね用鋼線材、およびばね - Google Patents
疲労特性に優れたばね用鋼線材、およびばね Download PDFInfo
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- WO2015115574A1 WO2015115574A1 PCT/JP2015/052595 JP2015052595W WO2015115574A1 WO 2015115574 A1 WO2015115574 A1 WO 2015115574A1 JP 2015052595 W JP2015052595 W JP 2015052595W WO 2015115574 A1 WO2015115574 A1 WO 2015115574A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
Definitions
- the present invention relates to a spring steel wire rod excellent in fatigue characteristics and a spring.
- springs such as valve springs and suspension springs are required to have improved fatigue characteristics. Further improvement in fatigue characteristics is also demanded in steel wires for springs such as a rolled material used as the material and a drawn material obtained by drawing the rolled material. In particular, there is a strong demand for improving fatigue characteristics in steel wires for valve springs.
- Non-Patent Document 1 discloses that in a valve spring steel, the inclusion composition is controlled to an amorphous stable composition such as CaO—Al 2 O 3 —SiO 2 or MnO—Al 2 O 3 —SiO 2. It is described that deformation during hot working is promoted and does not serve as a starting point for fatigue fracture and improves fatigue characteristics.
- Patent Document 1 proposes a technique in which the entire inclusion is easily deformed with a low melting point, and hard SiO 2 is not easily generated even if phase separation occurs during heating before or during hot rolling.
- Patent Document 2 proposes a technique for promoting the miniaturization by generating a large number of fine crystals in the inclusions to promote the division of the inclusions during hot rolling.
- Patent Document 3 discloses that at least one of LiO 2 , Na 2 O, and K 2 O is actively used in order to lower the melting point and viscosity of the complex oxide inclusions that are produced, and finally refine them.
- Patent Document 4 describes that the addition of ZrO 2 as an unprecedented oxide component contributes to the maintenance of the amorphous phase.
- Patent Document 5 discloses that B 2 O 3 is a complex oxide (for example, a CaO—Al 2 O 3 —SiO 2 complex oxide or a CaO—Al 2 O 3 —SiO 2 —MgO complex oxide). It is described that the oxide inclusions can be finely divided and the wire drawing workability and fatigue strength can be remarkably improved.
- Patent Document 3 Li having strong deoxidizing power is positively added as an origin of oxide inclusions.
- the Li 2 O concentration in inclusions cannot be measured by the conventional EPMA (Electron Probe X-ray Micro Analyzer), and therefore, an analysis method based on SIMS (Secondary Ion Mass Spectrometry) is uniquely developed. There is a difficulty in manufacturing as described in the above. Further, ZrO 2 described in Patent Document 4 and B 2 O 3 described in Patent Document 5 were found to have a risk of deteriorating fatigue properties according to the results of experiments by the present inventors. .
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a spring steel wire rod and a spring that are extremely excellent in fatigue characteristics.
- the steel wire rod for springs having excellent fatigue characteristics according to the present invention that has solved the above-mentioned problems, C: 0.2 to 1.2% (% means mass%, hereinafter the same unless otherwise specified), Si: 1.0-3%, Mn: 0.1-2%, Cr: 3% or less (excluding 0%), Al: 0.0002 to 0.005%, Ca: 0.0002 to 0.002%, Ti: 0.0003 to 0.010%
- the balance consists of iron and inevitable impurities
- the average composition of oxide inclusions having a minor axis of 1 ⁇ m or more present in a cross section parallel to the longitudinal direction of the steel material is mass%, CaO: 35% or less (including 0%), Al 2 O 3 : 40% or less (including 0%), SiO 2 : 30 to 95%, MgO: 8% or less (including 0%), MnO: 5 % Or less (including 0%), TiO 2 : 3 to 10%, and CaO + Al 2 O 3 + SiO 2 + MgO + MnO +
- the average composition of oxide inclusions is CaO: 10 to 35%, Al 2 O 3 : 10 to 40%, SiO 2 : 30 to 70%, MgO: 8% or less (including 0%), MnO : 5% or less (including 0%), TiO 2 : 3 to 10%, and CaO + Al 2 O 3 + SiO 2 + MgO + MnO + TiO 2 ⁇ 80% and a minor axis of 2 ⁇ m or more existing in the cross section
- the number of inclusions is preferably more than 0.002 / mm 2 .
- the average composition of the oxide inclusions is mass%, ZrO 2 : less than 1% (not including 0%), Na 2 O: less than 5% (not including 0%) ).
- the spring steel wire rod may further contain Ni: 0.5% or less (not including 0%), Cu: 0.5% or less (not including 0%).
- the spring steel wire rod may further contain V: 0.5% or less (excluding 0%).
- the spring having excellent fatigue characteristics that can solve the above problems has a gist in that it is a spring obtained by using the steel wire for spring.
- the chemical composition of the spring steel wire rod and the composition and number of oxide inclusions are appropriately controlled, a spring steel wire rod having extremely excellent fatigue characteristics can be obtained.
- Patent Documents 1 to 3 The inventors of the present invention have made extensive studies in order to provide a steel wire for springs that is extremely excellent in fatigue characteristics even after the disclosure of Patent Documents 1 to 3 and the like.
- amorphous amorphous SiO 2 such as SiO 2 —CaO—Al 2 O 3 —MgO—MnO.
- Patent Document 2 discloses a method for controlling the crystallization state (precipitating a fine crystal phase without completely crystallizing). The technology is proposed.
- the oxide-based inclusion containing TiO 2 based on SiO 2 —CaO—Al 2 O 3 —MgO—MnO has an average composition of mass% and CaO + Al 2 O 3 + SiO 2 + MgO + MnO + TiO 2 ⁇ 80 % Is satisfied.
- 80% or more in total in addition to the effects of oxide inclusions based on SiO 2 —CaO—Al 2 O 3 —MgO—MnO as reported in the above patent document, The effect of TiO 2 is exhibited.
- TiO 2 when TiO 2 is contained in the oxide inclusions obtained by Si deoxidation, it is separated into two phases of a TiO 2 concentrated phase (A phase) and a SiO 2 concentrated phase (B phase).
- the reason for separating into two phases is considered that TiO 2 has a property of separating into two liquid phases with SiO 2 at the molten steel stage.
- SiO 2 is SiO 2 concentration in the concentrated phase (B phase) increases, occur in Si-deoxidized steel easily Gehlenite (Gehlenite), crystal structure formation, such as spinel (Spinel, MgO ⁇ Al 2 O 3) Is suppressed.
- Patent Documents 1 to 5 described above do not disclose the above-described characteristic portions of the present invention.
- TiO 2 is cited as an impurity of inclusions, but it is completely described that fatigue characteristics are improved by controlling the amount of TiO 2 within a predetermined range as in the present invention. Absent.
- all the examples of Patent Document 4 disclose only an example containing 1.0% of impurities such as FeO and TiO 2 , and in this case, the effect of improving the fatigue characteristics by adding TiO 2 is obtained. (See No. 14 in the table below).
- the composition of oxide inclusions is different from the present invention in that it contains 1% or more of ZrO 2 .
- the present invention includes Ti as a component in steel in the range of 0.0003 to 0.010%, and the oxide-based intervening of SiO 2 —CaO—Al 2 O 3 —MgO—MnO. It is characterized in that TiO 2 is contained in the range of 3 to 10%.
- the steel wire for spring includes both a steel material after rolling (rolled material) and a wire drawing material obtained by drawing the rolled material. In the present invention, these are collectively referred to as “steel wire”.
- the oxide inclusion means an oxide inclusion in which an oxide forming element such as Ca, Al, Si, Ti, Mn, Mg, Na, Cr, Zr and oxygen are combined.
- the oxide inclusions are observed with an electron microscope, and energy dispersive X-ray analyzer (Energy Dispersive X-ray spectroscopy; EDX) or wavelength dispersive X-ray analyzer (Wavelength-Dispersive X-ray spectroscopy; WDX). Can be measured. Details of the measurement method will be described later.
- the average composition of the oxide inclusions having a minor axis of 1 ⁇ m or more present in a cross section parallel to the longitudinal direction of the steel material is mass%, CaO: 35% or less (including 0%), Al 2 O 3 : 40% or less (including 0%), SiO 2 : 30 to 95%, MgO: 8% or less (including 0%), MnO: 5 % Or less (including 0%), TiO 2 : 3 to 10%, and CaO + Al 2 O 3 + SiO 2 + MgO + MnO + TiO 2 ⁇ 80%, preferably CaO: 10 to 35%, Al 2 O 3 : 10 to 40 %, SiO 2 : 30 to 70%, MgO: 8% or less (including 0%), MnO: 5% or less (including 0%), TiO 2 : 3 to 10%, and CaO + Al 2 O 3 + SiO 2 + M
- the average composition of the oxide inclusions having a minor axis of 1 ⁇ m or more present in a cross section parallel to the longitudinal direction of the steel material is mass%, CaO: 35% or less (including 0%), Al 2 O 3 : 40% or less (including 0%), SiO 2 : 30 to 95%, MgO: 8% or less (including 0%), MnO: 5 % Or less (including 0%), TiO 2 : 3 to 10%, and CaO + Al 2 O 3 + SiO 2 + MgO + MnO + TiO 2 ⁇ 80%, the number of oxide inclusions having a minor axis of 2 ⁇ m or more present in the cross section Is more than 0.002 piece / mm 2 .
- CaO 35% or less
- CaO is a basic oxide, and when it is contained in SiO 2 that is an acidic oxide, the liquidus temperature of the oxide is lowered and has the effect of suppressing crystallization of oxide inclusions. You may contain in. Desirably, it is 10% or more, more preferably 15% or more. However, if the CaO content is too high, the oxide inclusions will crystallize, so the upper limit is made 35% or less. The upper limit of the CaO content is preferably 30% or less.
- SiO 2 is an acidic oxide and is an indispensable component for amorphizing oxide inclusions.
- the lower limit of the SiO 2 content is set to 30% or more.
- the lower limit of the SiO 2 content is preferably 40% or more.
- the upper limit of the SiO 2 content is 95% or less, preferably 70% or less, more preferably 50% or less.
- Al 2 O 3 is an amphoteric oxide, and if it is contained in SiO 2 that is an acidic oxide, the liquidus temperature of the oxide is lowered and has the effect of suppressing crystallization of the oxide. May be included. Desirably, it is 10% or more, More preferably, it is 20% or more.
- the upper limit of the Al 2 O 3 content exceeds 40%, an Al 2 O 3 crystal phase such as corundum crystallizes in the molten steel and in the solidification process, or an MgO ⁇ Al 2 O 3 crystal phase such as spinel together with MgO. Crystallizes out. In addition, these crystal phases are generated in the rolling temperature range. These solid phases are hard and remain as coarse inclusions, deteriorating fatigue properties. From such a viewpoint, the upper limit of the Al 2 O 3 content needs to be 40% or less, preferably 30% or less.
- MgO 8% or less (including 0%)
- MgO is not an essential oxide in the present invention, but has an effect of controlling the SiO 2 oxide to an optimum composition and lowering its melting point.
- the lower limit of the MgO content is preferably 0.2% or more.
- the MgO content is excessively high, the melting point of the SiO 2 -based oxide becomes high or MgO-based crystals are generated, so the upper limit is made 8% or less.
- it is 5% or less, More preferably, it is 3% or less.
- MnO 5% or less (including 0%)
- MnO is not an essential oxide in the present invention, like MgO, but MnO has an effect of lowering the melting point of the SiO 2 oxide.
- the lower limit of the MnO content is preferably 0.1% or more, more preferably 0.5% or more.
- the upper limit of the MnO content is 5% or less.
- TiO 2 is an oxide component that characterizes the present invention. As described above, when TiO 2 is contained in SiO 2 which is an acidic oxide, it is separated into two phases of TiO 2 concentrated phase (A phase) and SiO 2 concentrated phase (B phase). Has a quality-inhibiting action. As a result, it is possible to suppress crystallization during hot working of SiO 2 -containing oxide inclusions obtained from Si deoxidized steel, and to suppress cavities generated at the interface between the steel and oxide inclusions, and fatigue The characteristics are further improved. Since such an effect is obtained by controlling the lower limit of the TiO 2 content to 3% or more, the TiO 2 content is set to 3% or more.
- the TiO 2 content is 4% or more, More preferably, it is 5% or more.
- the upper limit of the TiO 2 content is 10% or less. Preferably it is 8% or less, More preferably, it is 7% or less.
- the oxide inclusions contained in the spring steel wire of the present invention are basically CaO, Al 2 O 3 , SiO 2 , MgO, MnO, and TiO 2 , and the balance is impurities.
- the impurities include impurities inevitably included in the manufacturing process.
- the impurities can be included as long as desired fatigue characteristics can be obtained without adversely affecting the crystallization state and form of the oxide inclusions.
- the total amount of the impurities needs to be controlled to 20% or more at the maximum.
- the impurities include ZrO 2 , Na 2 O, Cr 2 O 3 and the like.
- ZrO 2 is preferably reduced as much as possible because the concentration of the oxide inclusions increases and the crystallization of the inclusions is promoted to deteriorate the fatigue characteristics.
- the preferred content of ZrO 2 is less than 1%, more preferably 0.5% or less, and most preferably not contained.
- Na 2 O has a wider tolerance than ZrO 2 and may be contained if it is about 5%.
- the content and total amount of each oxide are controlled as described above, and the number of oxide inclusions having a minor axis of 2 ⁇ m or more needs to satisfy more than 0.002 / mm 2. is there. This ensures high fatigue properties and improves homogeneity.
- the number of oxide inclusions having a minor axis of 2 ⁇ m or more is preferably 0.005 pieces / mm 2 or more, more preferably 0.01 pieces / mm 2 or more, still more preferably 0.05 pieces / mm. 2 or more.
- the “oxide inclusion” is an oxide in which an oxide-forming element such as Ca, Al, Si, Ti, Mn, Mg, Na, Cr, and Zr is combined with oxygen. It means an inclusion and is not limited to the above-described oxides (CaO, Al 2 O 3 , SiO 2 , MgO, MnO, TiO 2 ). Further, among the oxide inclusions, “minor axis of 2 ⁇ m or more” is particularly defined because oxide inclusions having a minor axis of less than 2 ⁇ m have a relatively small adverse effect on fatigue characteristics.
- C is an element necessary for ensuring a predetermined strength.
- the content of C is set to 0.2% or more. Preferably it is 0.5% or more.
- the upper limit is made 1.2% or less.
- the upper limit with preferable C amount is 0.8% or less, More preferably, it is 0.7% or less.
- Si is an important element that contributes to increasing the strength of the steel wire rod for spring and improving the fatigue characteristics. Furthermore, it is an element that increases softening resistance and is useful for improving sag resistance. Furthermore, Si is an essential element for controlling the composition of the desired oxide inclusions. In order to effectively exhibit such an action, the Si content is set to 1.0% or more. A preferable Si content is 1.4% or more, and more preferably 1.8% or more. However, when the Si content is excessive, hard pure SiO 2 may be generated during solidification, and surface decarburization and surface flaws may increase and fatigue characteristics may deteriorate. Therefore, the upper limit of Si content is 3% or less. Preferably it is 2.4% or less, More preferably, it is 2.2% or less.
- Mn 0.1-2%
- Mn is an element that enhances hardenability and contributes to strength improvement.
- the lower limit of the Mn content is set to 0.1% or more. Preferably it is 0.5% or more. However, if the amount of Mn becomes excessive, the toughness and ductility decrease, so the upper limit is made 2% or less. More preferably, it is 1% or less.
- Cr 3% or less (excluding 0%)
- Cr is an element that improves the matrix strength of the spring steel wire rod by solid solution strengthening. Further, Cr, as well as Mn, works effectively to improve hardenability.
- the amount of Cr is preferably 0.5% or more, more preferably 0.9% or more. However, if the Cr content is excessive, the spring steel wire is likely to become brittle and the sensitivity of oxide inclusions increases, so that the fatigue characteristics are degraded. Therefore, the upper limit of Cr content is 3%.
- the upper limit with preferable Cr amount is 2% or less, More preferably, it is 1% or less.
- Al 0.0002 to 0.005%
- the Al content is 0.005% or less, preferably 0.002% or less, more preferably 0.0015% or less.
- the lower limit of the Al content is 0.0002% or more, preferably 0.0005% or more.
- Ca is a component contained in the wire steel material by slag refining for controlling the oxide inclusion composition.
- it is an element effective in improving fatigue characteristics by controlling the CaO content in oxide inclusions and suppressing crystallization of oxide inclusions.
- the Ca content is 0.0002% or more, preferably 0.0003% or more, more preferably 0.0005% or more.
- the Ca content becomes excessive and 0.00 If it exceeds 2%, the proportion of CaO becomes too high and the oxide crystallizes. Therefore, the Ca content is 0.002% or less, preferably 0.001% or less, more preferably 0.0008% or less.
- Ti is an element that characterizes the present invention.
- the Ti content needs to be 0.0003% or more.
- it is 0.0005% or more, More preferably, it is 0.0008% or more.
- the Ti content is 0.010% or less.
- it is 0.0050% or less, more preferably 0.0030% or less.
- the elements in steel used in the present invention are as described above, and the balance is iron and inevitable impurities.
- the inevitable impurities include elements that are brought in depending on the situation such as raw materials, materials, and manufacturing equipment, such as S, P, H, and N.
- Ni 0.5% or less (excluding 0%)
- Ni is an element that is effective in suppressing ferrite decarburization that occurs during hot rolling during the production of spring steel wire rods and heat treatment during spring production. Furthermore, Ni has the effect
- the lower limit of the preferable amount of Ni is 0.05% or more, more preferably 0.15% or more, and further preferably 0.2% or more.
- the upper limit of the Ni amount is preferably 0.5% or less, more preferably 0.3% or less.
- Cu 0.5% or less (excluding 0%)
- Cu is an element effective for suppressing ferrite decarburization that occurs during hot rolling at the time of manufacturing the steel wire rod for spring and heat treatment at the time of manufacturing the spring, and therefore may be included in an amount of 0.05% or more.
- the upper limit is preferably 0.5% or less, more preferably 0.3% or less.
- V 0.5% or less (excluding 0%)
- V is an element useful for improving hydrogen embrittlement resistance and fatigue characteristics by forming fine carbides or nitrides by combining with carbon, nitrogen, or the like. Furthermore, V is an element that contributes to improvements in spring toughness, yield strength, sag resistance, and the like due to the effect of crystal grain refinement.
- the lower limit of the V amount is preferably 0.05% or more, more preferably 0.10% or more. However, if the amount of V is excessive, the amount of carbide not dissolved in austenite during quenching heating increases, making it difficult to obtain sufficient strength and hardness, leading to coarsening of nitrides and fatigue breakage. It becomes easy. On the other hand, when the amount of V becomes excessive, the amount of retained austenite increases and the hardness of the spring decreases. Therefore, the preferable upper limit of the V amount is 0.5% or less, more preferably 0.4% or less.
- the present invention it is important to pay attention to each step of the melting process and hot working so that the desired composition and number of oxide inclusions can be obtained.
- the other steps are not particularly limited, and a method usually used for producing a spring steel wire can be appropriately selected and used.
- the preferred melting process and hot process used in the present invention are as follows.
- a predetermined amount of TiO 2 is contained as an oxide inclusion, but this control method is not particularly limited, either in the steel during smelting based on the method usually used in the technical field of the present invention.
- Ti may be added so that the amount of Ti is controlled within the range of 0.0003 to 0.010%.
- the addition method of Ti is not specifically limited, For example, you may adjust by adding the iron-type alloy containing Ti, or you may control Ti concentration in molten steel by control of a slag composition.
- the obtained slab is heated to 1100 to 1300 ° C. in a heating furnace and then subjected to block rolling at 900 to 1200 ° C. Thereafter, it is rolled at 800 to 1100 ° C. and hot rolled to a desired diameter.
- the spring steel material of the present invention can be obtained.
- it may be further drawn to obtain a spring steel wire material.
- the drawing condition is not particularly limited, and a commonly used method can be adopted.
- the spring steel wire rod of the present invention is very useful as a material for processed products that require high fatigue characteristics.
- the processed product include springs such as valve springs, clutch springs, brake springs and suspension springs used for automobile engines and suspensions; steel wires such as steel cords and the like.
- the manufacturing method of the spring is not particularly limited, and can be manufactured by a conventional method. Specifically, the spring steel wire rod is annealed as necessary, and then subjected to a cutting process, a lead patenting process, a wire drawing process, and an oil temper process to manufacture a spring.
- the obtained slab was heated at a temperature of 1100 to 1300 ° C. in a heating furnace and then subjected to block rolling at 900 to 1200 ° C. Thereafter, hot rolling was performed at 830 to 1100 ° C. to obtain a hot rolled material having a diameter of 8.0 mm.
- the hot-rolled material thus obtained (diameter: 8.0 mm) is 20 mm L (L is the length in the rolling direction) in the longitudinal direction (corresponding to the rolling direction) so as to include the central axis of the hot-rolled material. )
- One of the above micro samples was cut out and the cross section including the central axis was polished. The polished surface was observed using an electron probe X-ray microanalyzer (EPMA, trade name “JJA-8500F”) manufactured by JEOL Datum Co., Ltd.
- the composition of the component inclusions was quantitatively analyzed.
- the observation area of the polished surface was 100 to 1000 mm 2 and the component composition at the center of the oxide inclusion was quantitatively analyzed by wavelength dispersion spectroscopy of characteristic X-rays.
- the analysis target elements are Ca, Al, Si, Ti, Mn, Mg, Na, Cr, and Zr.
- the relationship between the X-ray intensity and the element concentration of each element is obtained in advance as a calibration curve and analyzed.
- the amount of elements contained in each sample was determined from the X-ray intensity obtained from the target oxide inclusions and the calibration curve, and the average composition of the oxide inclusions was determined by oxide conversion.
- Ti oxide can have a plurality of valences, but all were calculated as TiO 2 .
- the value obtained by dividing the number of oxide inclusions having a minor axis of 2 ⁇ m or more among the oxide inclusions present in the polished surface by the observation area (100 to 1000 mm 2 ) is The number of inclusions (pieces / mm 2 ) was used.
- test No. of Table 2 Is the same number of the test steel No. 1 in Table 1. Indicates that was used.
- Test No. in Table 2 1 to 11, 17, and 18 all satisfy the chemical composition and oxide composition defined in the present invention, and are found to be excellent in fatigue characteristics.
- the amount of Si and the amount of Al are within the scope of the present invention, but the amount of CaO in the oxide inclusions is increased because the amount of Si and the amount of Al are relatively low. .
- the amount of Ti and the amount of Al are within the scope of the present invention, but these amounts are contained in a relatively larger amount than the other examples, so the amount of SiO 2 in the oxide inclusions is reduced. As a result, the fatigue characteristics deteriorated.
- Test No. No. 14 had a small amount of Ti, so the amount of TiO 2 in the oxide inclusions was small, and the fatigue characteristics deteriorated.
- Test No. No. 15 had a large amount of Ti, so the amount of TiO 2 in the oxide inclusions increased and the fatigue characteristics deteriorated.
- the steel wire for springs of the present invention has better fatigue characteristics than before, and is suitable for valve springs, suspension springs and the like.
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Abstract
Description
域に制御して微細化する方法、熱間圧延時に介在物を延伸して分断させる方法などが提案されている。
C :0.2~1.2%(%は質量%の意味、以下、特に断らない限り、同じ)、
Si:1.0~3%、
Mn:0.1~2%、
Cr:3%以下(0%を含まない)、
Al:0.0002~0.005%、
Ca:0.0002~0.002%、
Ti:0.0003~0.010%
を含有し、残部は鉄及び不可避的不純物からなり、
鋼材の長手方向に平行な断面に存在する短径が1μm以上の酸化物系介在物の平均組成が質量%で、
CaO:35%以下(0%を含む)、Al2O3:40%以下(0%を含む)、SiO2:30~95%、MgO:8%以下(0%を含む)、MnO:5%以下(0%を含む)、TiO2:3~10%、および、CaO+Al2O3+SiO2+MgO+MnO+TiO2≧80%を満足すると共に前記断面に存在する短径2μm以上の酸化物系介在物の個数が0.002個/mm2超であるところに要旨を有する。
CaOは塩基性酸化物であり、酸性酸化物であるSiO2に含まれると、酸化物の液相線温度が下がり、酸化物系介在物の結晶化を抑制する効果があるため、介在物中に含有しても良い。望ましくは、10%以上、さらに好ましくは15%以上である。しかしながら、CaO含有量が高すぎると、酸化物系介在物が結晶化してしまうため、その上限を35%以下とする。CaO含有量の上限は、好ましくは30%以下である。
SiO2は酸性酸化物であり、酸化物系介在物を非晶質化させるために不可欠の成分である。このような効果を有効に発揮させるためには、SiO2含有量の下限を30%以上とする。SiO2含有量の下限は、好ましくは40%以上である。しかしながら、SiO2含有量が95%を超えると上記介在物の延伸性は低下して空洞も生成しやすくなり、疲労特性が悪化する。そのため、SiO2含有量の上限は95%以下とし、好ましくは70%以下、より好ましくは50%以下である。
Al2O3は両性酸化物であり、酸性酸化物であるSiO2に含まれると、酸化物の液相線温度が下がり、酸化物の結晶化を抑制する効果があるため、介在物中に含んでも良い。望ましくは10%以上、さらに好ましくは20%以上である。一方、Al2O3含有量の上限が40%を超えると、溶鋼中および凝固過程でコランダム等のAl2O3結晶相が晶出したり、MgOと共にスピネル等のMgO・Al2O3結晶相が晶出する。また、圧延温度域で、これらの結晶相が生成する。これらの固相は硬質であり、粗大な介在物として残留し、疲労特性を悪化させる。こうした観点から、Al2O3含有量の上限は40%以下とする必要があり、好ましくは30%以下である。
MgOは、本発明において必須の酸化物ではないが、SiO2系酸化物を最適な組成に制御して、その融点を低下させる効果がある。このような作用を有効に発揮させるため、MgO含有量の下限は、好ましくは0.2%以上である。ただし、MgO含有量が多くなり過ぎると、SiO2系酸化物の融点が高くなったり、MgO系の結晶が生成するため、その上限を8%以下とする。好ましくは5%以下、より好ましくは3%以下である。
MnOも上記MgOと同様、本発明において必須の酸化物ではないが、MnOは、SiO2系酸化物の融点を低下させる効果がある。このような作用を有効に発揮させるため、MnO含有量の下限は、好ましくは0.1%以上、より好ましくは0.5%以上である。ただし、本発明のようにSiを1.0%以上含む高Si鋼においてMnOをあまり高濃度に制御することは現実的でないため、MnO含有量の上限は5%以下とする。
TiO2は、本発明を特徴付ける酸化物成分である。前述したようにTiO2が酸性酸化物であるSiO2に含まれると、TiO2濃化相(A相)とSiO2濃化相(B相)の2相に分離し、両相とも、結晶質化抑制作用を有する。その結果、Si脱酸鋼で得られるSiO2含有酸化物系介在物の熱間加工時の結晶化の抑制、鋼と酸化物系介在物との界面に発生する空洞の抑制を実現でき、疲労特性が一層向上する。このような効果は、TiO2含有量の下限を3%以上に制御することによって得られるため、TiO2含有量は3%以上とする。好ましくは4%以上、より好ましくは5%以上である。しかしながら、TiO2含有量が多くなりすぎると、TiO2系酸化物が結晶相として単独で生成するため、疲労特性が低下する。そのため、TiO2含有量の上限を10%以下とする。好ましくは8%以下、より好ましくは7%以下である。
本発明では、各酸化物の含有量を上記のように制御すると共に、これらの含有量の合計を80%以上に制御することが必要であり、これにより、酸化物系介在物の非晶質が保持され、疲労特性が向上する。上記酸化物の合計量は多いほど良く、好ましくは90%以上、である。最も好ましくは100%である。
本発明では、上記のように各酸化物の含有量および合計量を制御すると共に、短径2μm以上の酸化物系介在物の個数が0.002個/mm2超を満足することが必要である。これにより、高い疲労特性が確保され、均質性も向上する。短径2μm以上の酸化物系介在物の個数は、好ましくは0.005個/mm2以上であり、より好ましくは0.01個/mm2以上であり、更に好ましくは0.05個/mm2以上である。ここで、上記「酸化物系介在物」とは、前述したように、Ca、Al、Si、Ti、Mn、Mg、Na、Cr、Zrなどの酸化物形成元素と酸素とが結合した酸化物介在物を意味し、上述した酸化物(CaO、Al2O3、SiO2、MgO、MnO、TiO2)に限定されない。また、上記酸化物系介在物のうち、特に「短径2μm以上」を規定したのは、短径2μm未満の酸化物系介在物は、疲労特性に対する悪影響が比較的少ないためである。
Cは、所定の強度を確保するために必要な元素であり、このような特性を有効に発揮させるためには、Cの含有量は0.2%以上とする。好ましくは0.5%以上である。但し、C含有量が過剰になるとばね用鋼線材が脆化し、実用的でなくなるので、その上限を1.2%以下とする。C量の好ましい上限は0.8%以下、より好ましくは0.7%以下である。
Siは、ばね用鋼線材の高強度化、および疲労特性の向上に寄与する重要な元素である。更に、軟化抵抗を高め、耐へたり性の向上にも有用な元素である。さらに、所望とする酸化物系介在物の組成に制御するためにもSiは必須の元素である。このような作用を有効に発揮させるため、Si含有量を1.0%以上とする。好ましいSi含有量は、1.4%以上であり、より好ましくは1.8%以上である。しかしながら、Si含有量が過剰になると、凝固中に硬質な純SiO2が生成するおそれがあり、表面脱炭や表面疵が増加して疲労特性が低下する場合がある。そのため、Si量の上限を3%以下とする。好ましくは2.4%以下、より好ましくは2.2%以下である。
Mnは、脱酸剤として作用するほか、焼入れ性を高めて強度向上にも寄与する元素である。このような作用を有効に発揮させるため、Mn含有量の下限を0.1%以上とする。好ましくは0.5%以上である。但し、Mn量が過剰になると、靭性や延性が低下するため、その上限を2%以下とする。より好ましくは1%以下である。
Crは、固溶強化によりばね用鋼線材のマトリックス強度を向上させる元素である。さらにCrは、Mnと同様、焼入れ性向上にも有効に作用する。Cr量は、好ましくは0.5%以上、より好ましくは0.9%以上である。しかし、Crが過剰であるとばね用鋼線材が脆化しやすくなって酸化物系介在物の感受性が増大するため、疲労特性が低下する。そこでCr量の上限を3%とする。Cr量の好ましい上限は2%以下、より好ましくは1%以下である。
Al含有量が多くなり、特に0.005%を超えると、Al2O3を主体とする硬質な酸化物の生成量が多くなり、更に圧下した後も粗大な酸化物として残存するので、疲労特性が低下する。従って、Alの含有量を0.005%以下とし、好ましくは0.002%以下、より好ましくは0.0015%以下である。但し、Al含有量を0.0002%未満にすると、酸化物系介在物中のAl2O3含有量が少なくなり過ぎ、SiO2を多く含む結晶相が生成する。従って、Al含有量の下限は0.0002%以上とし、好ましくは0.0005%以上である。
Caは、酸化物系介在物組成制御のためのスラグ精錬により、線鋼材中に含有される成分である。本発明においては、酸化物系介在物中のCaO含有量を制御し、酸化物系介在物の結晶化を抑制して、疲労特性の改善に有効な元素である。このような効果を発揮させるため、Ca含有量は0.0002%以上とし、好ましくは0.0003%以上、より好ましくは0.0005%以上である。しかしながら、Ca含有量が過剰になって0.00
2%を超えると、CaOの割合が高くなり過ぎて、酸化物が結晶化してしまう。従って、Ca含有量は0.002%以下とし、好ましくは0.001%以下、より好ましくは0.0008%以下である。
Tiは、本発明を特徴付ける元素である。所定量のTiを添加し、酸化物系介在物中のTiO2含有量を適切に制御することにより、上記介在物の非晶質安定性がより高められ、疲労特性が一層向上する。このような効果を得るためには、Ti含有量は0.0003%以上とする必要がある。好ましくは0.0005%以上、より好ましくは0.0008%以上である。ただし、Tiの含有量が多くなって0.010%を超えると、TiO2系酸化物が結晶相として単独で生成してしまう。従って、Ti含有量は0.010%以下とする。好ましくは、0.0050%以下、より好ましくは0.0030%以下である。
Niは、ばね用鋼線材製造時の熱間圧延やばね製造時の熱処理の際に生ずるフェライト脱炭の抑制に有効な元素である。更にNiは、焼入・焼戻し後のばねの靱性を高める作用を有する。好ましいNi量の下限は、0.05%以上、より好ましくは0.15%以上、更に好ましくは0.2%以上である。一方、Ni量が過剰になると、焼入・焼戻し処理で残留オーステナイト量が増大し、引張強さが低下する。そこでNi量の上限は、好ましくは0.5%以下、より好ましくは0.3%以下とする。
Cuは、ばね用鋼線材製造時の熱間圧延やばね製造時の熱処理の際に生ずるフェライト脱炭の抑制に有効な元素であるため、0.05%以上含んでも良い。上限は、好ましくは0.5%以下、より好ましくは0.3%以下とする。
Vは、炭素や窒素等と結合して微細な炭化物や窒化物等を形成し、耐水素脆性や疲労特性の向上に有用な元素である。更にVは、結晶粒微細化効果により、ばねの靱性、耐力、耐へたり性などの向上に寄与する元素である。V量の下限は、好ましくは0.05%以上、より好ましくは0.10%以上である。しかし、V量が過剰になると、焼入加熱時にオーステナイト中に固溶されない炭化物量が増大し、充分な強度や硬さが得られ難くなるほ
か、窒化物の粗大化を招き、疲労折損が生じ易くなる。またV量が過剰になると、残留オーステナイト量が増加し、ばねの硬さが低下する。そこで、V量の好ましい上限を0.5%以下、より好ましくは0.4%以下とする。
まず、Siによる脱酸を実施し、本発明で規定する組成となるようにC、Si、Mn、Cr、Ti、Al、Ni、Vを添加した後、常法に従い、CaO-SiO2系スラグを用いてスラグ精錬を実施して、CaO-Al2O3-SiO2-MgO-MnO-TiO2の組成に制御する。このとき、上記スラグを溶綱に十分懸濁することで、短径2μm以上の酸化物系介在物の個数を所定の範囲とすることができる。なお、本発明では、酸化物系介在物として所定量のTiO2を含有するが、この制御方法も特に限定されず、本発明の技術分野で通常用いられる方法に基づき、溶製時に、鋼中のTi量が0.0003~0.010%の範囲内に制御されるようにTiを添加すれば良い。Tiの添加方法は特に限定されず、例えば、Tiを含有する鉄系合金を添加して調整しても良いし、あるいは、スラグ組成の制御によって溶鋼中のTi濃度を制御しても構わない。
得られた鋳片を、加熱炉において1100~1300℃に加熱した後、900~1200℃で分塊圧延を実施する。その後、800~1100℃で圧延し、所望の径まで熱間圧延を実施する。
容量150kg/1chの小型溶解炉を用い、下記表1に示す各種化学成分の供試鋼を溶製し、φ245mm×480mmの鋳片を作製した。溶製に当たっては、溶製時にMgO系耐火物の坩堝を用い、C、Si、Mn、およびCrのほか、必要に応じてNiおよびVの少なくとも一種を添加して所定の濃度に調整した後、Ti→Caの順序で投入し、TiおよびCaの各濃度を調整した。本実施例では、溶鋼に添加するCaとしてNi-Ca
合金を、Ti源としてFe-Ti合金を、それぞれ用いた。このようにして得られた鋳片の化学成分を表1に示す。
このようにして得られた熱間圧延材(直径:8.0mm)について、当該熱間圧延材の中心軸を含むように、長手方向(圧延方向に相当)に20mmL(Lは圧延方向長さ)以上のミクロ試料を1個切り出し、上記中心軸を含む断面を研磨した。この研磨面を、日本電子データム社製の電子線マイクロプローブX線分析計(Electron ProbeX-ray Micro Analyzer;EPMA、商品名「JXA-8500F」)を用いて観察し、短径が1μm以上の酸化物系介在物について成分組成を定量分析した。研磨面の観察面積は100~1000mm2とし、酸化物系介在物の中央部での成分組成を特性X線の波長分散分光により定量分析した。分析対象元素は、Ca、Al、Si、Ti、Mn、Mg、Na、Cr、Zrとし、既知物質を用いて各元素のX線強度と元素濃度の関係を予め検量線として求めておき、分析対象とする上記酸化物系介在物から得られたX線強度と上記検量線から各試料に含まれる元素量を定量し、酸化物換算することで酸化物系介在物の平均組成を求めた。Ti酸化物は複数の価数をとりうるが、全てTiO2として計算した。
上記熱間圧延材(直径:8.0mm)を皮削りし、直径:7.4mmまで伸線した後、パテンティングを行い、直径:4.0mmまで冷間線引き加工した。次いで、油焼入れと、約450℃の鉛浴での焼戻しを連続して行なってオイルテンパー処理を行なった後、直径4.0mm×長さ650mmのワイヤを得た。このようにして得られたワイヤについて、400℃で歪取焼鈍相当処理を行なった後、ショットピーニングを行ない、200℃の
低温焼鈍を行い、疲労強度測定用試験片を作製した。
折損率(%)=[A/(A+B)]×100
本出願は、2014年1月29日出願の日本特許出願(特願2014-014633)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (4)
- C :0.2~1.2%(%は質量%の意味、以下、特に断らない限り、同じ)、
Si:1.0~3%、
Mn:0.1~2%、
Cr:3%以下(0%を含まない)、
Al:0.0002~0.005%、
Ca:0.0002~0.002%、
Ti:0.0003~0.010%
を含有し、残部は鉄及び不可避的不純物からなり、
鋼材の長手方向に平行な断面に存在する短径が1μm以上の酸化物系介在物の平均組成が質量%で、
CaO:35%以下(0%を含む)、Al2O3:40%以下(0%を含む)、SiO2:30~95%、MgO:8%以下(0%を含む)、MnO:5%以下(0%を含む)、TiO2:3~10%、および、CaO+Al2O3+SiO2+MgO+MnO+TiO2≧80%を満足すると共に、
前記断面に存在する短径2μm以上の酸化物系介在物の個数が0.002個/mm2超であることを特徴とする疲労特性に優れたばね用鋼線材。 - 更に、前記酸化物系介在物の平均組成が質量%で、ZrO2:1%未満(0%を含まない)、Na2O:5%未満(0%を含む)である請求項1に記載のばね用鋼線材。
- 更に、Ni:0.5%以下(0%を含まない)、Cu:0.5%以下(0%を含まない)及びV:0.5%以下(0%を含まない)の少なくとも一つを含有する請求項1または2に記載のばね用鋼線材。
- 請求項1~3のいずれかに記載のばね用鋼線材を用いて得られるばね。
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US15/115,185 US20160348221A1 (en) | 2014-01-29 | 2015-01-29 | Steel wire for springs having excellent fatigue properties, and spring |
MX2016009761A MX2016009761A (es) | 2014-01-29 | 2015-01-29 | Alambre de acero para resortes que tienen propiedades excelentes de fatiga, y resorte. |
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Cited By (4)
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WO2017170755A1 (ja) * | 2016-03-30 | 2017-10-05 | 株式会社神戸製鋼所 | 曲げ加工性に優れた熱処理鋼線 |
US11807923B2 (en) | 2020-06-17 | 2023-11-07 | Sumitomo Electric Industries, Ltd. | Spring steel wire |
US11892048B2 (en) | 2020-06-15 | 2024-02-06 | Sumitomo Electric Industries, Ltd. | Spring steel wire |
DE112022002968T5 (de) | 2021-08-05 | 2024-03-21 | Sumitomo Electric Industries, Ltd. | Stahldraht für Federn |
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JP2017160466A (ja) * | 2016-03-07 | 2017-09-14 | 株式会社神戸製鋼所 | 転動疲労特性に優れた軸受用鋼材、その製造方法及び軸受部品 |
KR20190119089A (ko) * | 2017-03-24 | 2019-10-21 | 닛폰세이테츠 가부시키가이샤 | 선재 및 평강선 |
CN107813433A (zh) * | 2017-05-15 | 2018-03-20 | 开封大学 | 一种ntc‑pv800h硅片切割机的特殊结构钢线硅片切割方法 |
DE112020000034T5 (de) * | 2019-07-01 | 2022-03-24 | Sumitomo Electric Industries, Ltd. | Stahldraht und Feder |
WO2021075501A1 (ja) * | 2019-10-16 | 2021-04-22 | 日本製鉄株式会社 | 弁ばね |
US20230085279A1 (en) * | 2020-02-21 | 2023-03-16 | Nippon Steel Corporation | Steel wire |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2017170755A1 (ja) * | 2016-03-30 | 2017-10-05 | 株式会社神戸製鋼所 | 曲げ加工性に優れた熱処理鋼線 |
US11892048B2 (en) | 2020-06-15 | 2024-02-06 | Sumitomo Electric Industries, Ltd. | Spring steel wire |
US11807923B2 (en) | 2020-06-17 | 2023-11-07 | Sumitomo Electric Industries, Ltd. | Spring steel wire |
DE112022002968T5 (de) | 2021-08-05 | 2024-03-21 | Sumitomo Electric Industries, Ltd. | Stahldraht für Federn |
KR20240045214A (ko) | 2021-08-05 | 2024-04-05 | 스미토모덴키고교가부시키가이샤 | 스프링용 강선 |
Also Published As
Publication number | Publication date |
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US20180320255A1 (en) | 2018-11-08 |
KR101815410B1 (ko) | 2018-01-04 |
CN105940132A (zh) | 2016-09-14 |
JP2018193615A (ja) | 2018-12-06 |
JP2015163735A (ja) | 2015-09-10 |
EP3101148A1 (en) | 2016-12-07 |
MX2016009761A (es) | 2016-11-17 |
CN105940132B (zh) | 2018-01-30 |
EP3101148A4 (en) | 2017-11-01 |
KR20160104026A (ko) | 2016-09-02 |
US20160348221A1 (en) | 2016-12-01 |
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