WO2013179934A1 - コイリング性と耐水素脆性に優れた高強度ばね用鋼線およびその製造方法 - Google Patents
コイリング性と耐水素脆性に優れた高強度ばね用鋼線およびその製造方法 Download PDFInfo
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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
-
- 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
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- 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
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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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
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- 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
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
-
- 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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- 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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/02—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant
- F16F1/021—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant characterised by their composition, e.g. comprising materials providing for particular spring properties
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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
- C21D2211/008—Martensite
Definitions
- the present invention relates to a steel wire for high-strength springs excellent in coiling property and hydrogen embrittlement resistance (hydrogen embrittlement resistance) and a method for producing the same.
- a steel wire for a spring for example, a coil spring
- a tempered (quenched and tempered) state has a high tensile strength of 1900 MPa or more, and is excellent in coiling and hydrogen brittleness, and a method for producing the same It is about.
- Coil springs used in automobiles are required to be lighter in order to reduce exhaust gas and improve fuel efficiency, and require higher strength. ing.
- the cold winding is performed by drawing a steel wire for a spring, quenching and tempering, cold coiling, and then sequentially performing strain relief annealing, setting, shot peening, and painting to produce a coil spring. It is a method to do.
- spring winding (coiling) is performed after quenching and tempering instead of adjusting the strength by quenching and tempering after spring winding as in the hot winding. Therefore, a steel wire with high strength and low workability is used for the spring winding process, and it is easy to break during the spring winding. Such a tendency becomes remarkable as the strength increases. Therefore, in the case of the cold winding, the steel wire after quenching and tempering used for the spring winding process is required to have excellent ductility (coiling property). In addition, since the high strength spring is likely to be hydrogen brittle, the spring steel wire used for manufacturing the spring is also required to have excellent hydrogen brittleness resistance.
- Patent Document 1 shows that the brittle fracture resistance can be improved by controlling the amount of solid solution C, the amount of Cr contained as a Cr-containing precipitate, and the TS value represented by a predetermined formula. ing.
- Patent Document 1 discloses, as a production method, plastic working with a true strain of 0.10 or more; average heating rate at 200 ° C. or higher: TK from 850 to 1100 ° C. at 20 K / s or higher, and then average cooling Speed: Quenching treatment for cooling to 200 ° C. or higher at 30 K / s or higher; Heating to a temperature (T2 ° C.) or higher determined by a predetermined formula with an average temperature rising rate at 300 ° C. or higher being 20 K / s or higher, and 300 ° C. or higher It is shown that a tempering process is performed in which the residence time t1 is set to 240 sec or less and further cooled to 300 ° C. or less.
- Patent Document 2 shows that the amount of retained austenite after quenching and tempering is suppressed to 20% by volume or less in order to ensure corrosion resistance in consideration of use in a corrosive environment.
- Patent Document 3 shows that coiling properties and fatigue characteristics can be improved by controlling the component composition and controlling the size and density of carbides and the prior austenite grain size number.
- Patent Document 4 shows that coiling property and hydrogen embrittlement resistance can be improved by controlling the prior austenite average particle size; and the amount of retained austenite, the average particle size and the maximum particle size. Yes.
- alloy elements such as Cr are suppressed from the viewpoint of cost reduction. Further, from the viewpoint of improving the corrosion fatigue characteristics by appropriately (shallowing) the shape of the corrosion pit generated in the corrosive environment, it is required to suppress the Cr amount.
- Patent Document 5 proposes that delayed fracture characteristics can be improved by controlling the grain size of the prior austenite crystal grains and the density of undissolved carbides of a certain size without making the alloy elements such as Cr essential. Has been.
- Patent Document 5 is mostly examples using Cr and are not based on the assumption that Cr is not used.
- an alloy element such as Cu, Ti, Nb or the like is used in an embodiment that does not contain Cr.
- Patent Document 5 Cr or other alloy elements (Cu, Ti, Nb) are used to ensure strength. Therefore, Patent Document 5 does not show that high strength can be achieved without using these Cr and the like.
- the present invention has been made paying attention to the above-mentioned circumstances, and the object thereof is a spring steel wire obtained by quenching and tempering by high-frequency heating, which does not use Cr, and is an alloy element such as Cu. Is to provide a steel wire for a spring that exhibits high strength of 1900 MPa or more and is excellent in coiling property and hydrogen brittleness resistance.
- the steel wire for a high-strength spring of the present invention that has solved the above problems has C: 0.40 to 0.65% (meaning of mass%, the same applies to chemical components), Si: 1.0 to 3.0 %, Mn: 0.6 to 2.0%, P: 0.015% or less (not including 0%), S: 0.015% or less (not including 0%), and Al: 0.001 to 0.10%, balance of iron and inevitable impurities, tempered martensite: 70 area% or more and residual austenite: 6 to 15 area%, and the method specified in JIS G-0551
- the prior austenite grain size number obtained in step (1) is 10.0 or more and the tensile strength is 1900 MPa or more.
- the steel wire for high-strength springs can ensure desired characteristics with the above component composition, but it is further shown in the following (a) and (b) for the purpose of providing further corrosion resistance and the like depending on the use. It may contain an element.
- A one or more elements selected from the group consisting of Cu: 0.05 to 1.5% and Ni: 0.05 to 1.5%;
- the present invention also includes a spring obtained using the steel wire for high strength springs.
- the present invention also includes a method for producing the steel wire for high-strength springs.
- the production method is characterized in that a steel material satisfying the above component composition is used and quenching and tempering performed after wire drawing is performed so as to satisfy all of the following quenching conditions and the following tempering conditions.
- Steel wire is obtained. Since the spring steel wire of the present invention does not use Cr as described above, the manufacturing cost can be suppressed and the corrosion resistance is excellent. Furthermore, since the spring steel wire of the present invention does not require an alloy element such as Cu as described above, the manufacturing cost of the steel wire can be further suppressed. As a result, a high-strength spring that hardly causes hydrogen embrittlement (for example, a coil spring such as a suspension spring, which is one of automotive parts) can be supplied at low cost.
- the inventors of the present invention have made extensive studies to obtain a spring steel wire that exhibits high strength and excellent coiling and hydrogen embrittlement resistance without using an alloy element such as Cr. It was.
- the composition consisting of basic components can be controlled without using expensive alloy elements, and in particular, the quenching and tempering conditions in the manufacturing process can be controlled to ensure the structure described below without reducing the strength.
- the inventors have found that the above excellent characteristics can be achieved and completed the present invention.
- the upper limit of the amount of retained austenite was set to 15 area%.
- the amount of retained austenite is preferably 13 area% or less.
- the prior austenite (old ⁇ ) grain size number determined by the method specified in JIS G 0551 is set to 10.0 or more.
- the old ⁇ grain size number is preferably 10.5 or more, more preferably 11.0 or more.
- the upper limit of the old ⁇ grain size number is about 14.0.
- the steel material (steel wire) of the present invention has a tempered martensite main body (70% by area or more as a percentage of the entire structure). In order to ensure high strength and high toughness, it is necessary to perform a quenching and tempering process described later to obtain a structure mainly composed of the tempered martensite.
- the tempered martensite is preferably 80 area% or more.
- Other structures may include bainite, ferrite, pearlite, etc., but these are 10 area% or less even if included. Preferably it is 0 area%.
- C is an element necessary for ensuring high strength, and is also an element effective for improving hydrogen embrittlement resistance by forming fine carbides. Therefore, C is contained at 0.40% or more.
- the amount of C is preferably 0.50% or more, more preferably 0.58% or more.
- C is also an element that deteriorates corrosion resistance. Therefore, it is necessary to suppress the amount of C in order to improve the corrosion fatigue characteristics of a spring product (such as a suspension spring) that is a final product. Therefore, in the present invention, the C content is set to 0.65% or less.
- the amount of C is preferably 0.62% or less.
- Si is an element necessary for ensuring strength and has an effect of making carbide fine. In order to exhibit such an effect effectively, it is necessary to contain Si 1.0% or more.
- the amount of Si is preferably 1.3% or more, more preferably 1.8% or more.
- Si is also an element that promotes decarburization. If Si is excessively contained, formation of a decarburized layer on the surface of the steel material is promoted in the manufacturing process of the steel wire. As a result, a peeling process is required to delete the decarburized layer, resulting in an increase in manufacturing cost. Therefore, in the present invention, the upper limit of the Si amount is set to 3.0%.
- the amount of Si is preferably 2.5% or less, more preferably 2.2% or less.
- Mn is an element useful for detoxification of S by forming M and S which are harmful elements in steel while being used as a deoxidizing element. It is also an element contributing to strength improvement. In order to exhibit these effects effectively, the amount of Mn is made 0.6% or more. The amount of Mn is preferably 0.7% or more, more preferably 0.8% or more. However, when Mn is contained excessively, the residual ⁇ amount is likely to increase more than necessary, and the hydrogen embrittlement resistance and ductility (coiling properties) are reduced. For these reasons, the Mn content is set to 2.0% or less in the present invention. The amount of Mn is preferably 1.6% or less, more preferably 1.3% or less.
- P 0.015% or less (excluding 0%)
- P is a harmful element that deteriorates the ductility (coiling property) of the steel material. Therefore, it is desirable that the amount of P is low, and the upper limit is 0.015%.
- the amount of P is preferably 0.010% or less, more preferably 0.008% or less.
- S 0.015% or less (excluding 0%)] S is also a harmful element that deteriorates the ductility (coiling property) of the steel material in the same manner as P described above. Therefore, it is desirable that the amount of S is low, and the upper limit is 0.015%.
- the amount of S is preferably 0.010% or less, more preferably 0.008% or less.
- Al is mainly added as a deoxidizing element. Further, N and AlN are formed to render the solid solution N harmless and contribute to the refinement of the structure. In order to fully exhibit these effects, the Al amount needs to be 0.001% or more.
- the amount of Al is preferably 0.002% or more.
- Al is an element that promotes decarburization as well as Si. Therefore, it is necessary to suppress the amount of Al in the spring steel wire containing a large amount of Si.
- the amount of Al is set to 0.10% or less.
- the amount of Al is preferably 0.07% or less, more preferably 0.030% or less, and still more preferably 0.020% or less.
- the components of the steel of the present invention are as described above, and the balance consists of iron and inevitable impurities.
- the spring steel wire of the present invention does not contain Cr as described above. Moreover, high strength and excellent coiling property and hydrogen embrittlement resistance can be achieved with the above component composition without using an alloy element such as Cu. Depending on the application, the following elements may be further contained for the purpose of providing further corrosion resistance and the like.
- Cu is an element effective for suppressing surface layer decarburization and improving corrosion resistance.
- the Cu content is preferably 0.05% or more, more preferably 0.2% or more.
- the amount of Cu is more preferably 1.3% or less, still more preferably 0.7% or less, and still more preferably 0.4% or less.
- the amount of Cu exceeds 0.5%, hot brittleness due to Cu can be prevented by making Ni equal to or more than Cu present [Ni amount (mass%) ⁇ Cu amount (mass%)]. Can be suppressed.
- Ni is an element effective for suppressing surface decarburization and improving corrosion resistance.
- the Ni content is preferably 0.05% or more.
- the amount of Ni is more preferably 0.2% or more.
- the Ni content is preferably 1.5% or less.
- the Ni content is more preferably 0.7% or less, and still more preferably 0.4% or less.
- Ti 0.10% or less (not including 0%), B: 0.010% or less (not including 0%), Nb: 0.10% or less (not including 0%), Mo: 0.0. 5% or less (excluding 0%), and V: one or more elements selected from the group consisting of 0.3% or less (not including 0%)]
- Ti is an element useful for forming a sulfide with S to make S harmless. Ti also has the effect of forming a carbonitride to refine the structure. In order to exhibit these effects, it is preferable to contain 0.02% or more of Ti. The amount of Ti is more preferably 0.05% or more. However, when the amount of Ti becomes excessive, coarse Ti sulfide is formed, and ductility may deteriorate. Therefore, in this invention, it is preferable to make Ti amount into 0.10% or less. From the viewpoint of cost reduction, it is more preferable to suppress the Ti amount to 0.07% or less.
- B is a hardenability improving element. B also has an effect of strengthening the austenite grain boundary and is an element contributing to the suppression of destruction. In order to exert these effects, the B content is preferably 0.0005% or more, more preferably 0.0010% or more. However, since the above effect is saturated even if B is added excessively, the amount of B is preferably 0.010% or less. The amount of B is more preferably 0.0050% or less.
- Nb is an element that forms carbonitrides with C and N and mainly contributes to refinement of the structure.
- the Nb content is preferably 0.003% or more, and more preferably 0.005% or more.
- the Nb amount is preferably 0.10% or less. From the viewpoint of cost reduction, the Nb content is more preferably suppressed to 0.07% or less.
- Mo is an element that forms carbonitrides with C and N in the same manner as Nb, and contributes to refinement of the structure. Mo is also an element effective for securing the strength after tempering. In order to sufficiently exhibit these effects, the Mo amount is preferably 0.15% or more, more preferably 0.20% or more. However, when the amount of Mo becomes excessive, coarse carbonitrides are formed and the ductility (coiling property) of the steel material is deteriorated. Therefore, the Mo amount is preferably 0.5% or less, and more preferably 0.4% or less.
- V is an element that effectively acts to increase the strength of steel by precipitation strengthening.
- V is an element that increases toughness and contributes to improvement of sag resistance, and refines crystal grains to improve strength and proof stress ratio.
- the V amount is preferably 0.03% or more, more preferably 0.05% or more, and further preferably 0.10% or more.
- the V amount is preferably 0.3% or less.
- the amount of V is more preferably 0.25% or less, still more preferably 0.22% or less, and still more preferably 0.20% or less.
- the spring steel wire of the present invention contains a certain amount of retained austenite.
- This retained austenite is a structure that is not a little present when carbon steel is generally quenched.
- the amount of C and the alloy component are increased in order to increase the strength of the steel material, the residual austenite that is present during quenching increases, and it is difficult to decompose during tempering, thereby securing the retained austenite.
- an alloy element effective for securing retained austenite is not essential.
- quenching and tempering are performed using a high-frequency heating device under the conditions described later (particularly, rapid heating and short-time heating are performed in quenching and tempering). As a result, the strength is increased and retained austenite is secured.
- the prior austenite crystal grains can be easily refined by performing the quenching and tempering described later using high-frequency heating as described above.
- [Quenching process] Average heating rate (HR1) from 100 ° C. to quenching heating temperature (T1): 40 ° C./s or more)
- the HR1 is set to 40 ° C./s or more.
- the HR1 is preferably 50 ° C./s or higher, more preferably 100 ° C./s or higher.
- the upper limit of HR1 is about 400 ° C./s from the viewpoint of temperature control.
- the average rate of temperature increase from room temperature to 100 ° C. is not particularly limited.
- the T1 is set to 1000 ° C. or less.
- the T1 is preferably 980 ° C. or lower, more preferably 930 ° C. or lower.
- the T1 is set to 850 ° C. or higher.
- the T1 is preferably 870 ° C. or higher, more preferably 900 ° C. or higher.
- the t1 is 90 seconds or less.
- the t1 is preferably 60 seconds or less, more preferably 40 seconds or less.
- this t1 should be 5 seconds or more.
- the t1 is more preferably 10 seconds or more, and still more preferably 15 seconds or more.
- the CR1 is set to 30 ° C./s or less.
- the CR1 is preferably 25 ° C./s or less, more preferably 20 ° C./s or less.
- the CR1 is set to 5 ° C./s or more.
- the CR1 is preferably 10 ° C./s or higher, more preferably 15 ° C./s or higher.
- the cooling method examples include water cooling (immersion in a water tank, etc.), spray cooling, mist cooling, cooling with He gas, etc., but the present invention is to be manufactured at a low cost, and from 300 ° C. to 80 ° C. Since it is necessary to control the average cooling rate (CR1) within the above range, the cooling at the time of quenching is preferably a method of adopting spray cooling or mist cooling and adjusting the water amount of the spray or mist.
- the cooling rate at the time of quenching is controlled relatively gently to ensure retained austenite.
- it cools to 200 degrees C or less by making average cooling rate CR1 after quenching heating into 30 K / s or more, and the amount of residual austenite is as small as 5% or less by volume ratio.
- the cooling at the time of quenching and tempering is water cooling
- Patent Document 3 the cooling after the quenching is water cooling, so both try to control the cooling at the time of quenching to ensure retained austenite. It is not what you do.
- the average cooling rate of 50 ° C./s or more is required for quenching. It is better to cool with.
- the cooling method include water cooling, spray cooling, mist cooling and the like.
- the HR2 is set to 30 ° C./s or more.
- the HR2 is preferably 40 ° C./s or higher, more preferably 50 ° C./s or higher.
- the HR2 is preferably 300 ° C./s or less, more preferably 200 ° C./s or less.
- the average rate of temperature increase from room temperature to 100 ° C. is not particularly limited.
- T2 Temporal heating temperature (T2): 350 to 550 ° C.) If the tempering heating temperature (T2) is too low, there is a problem that the tempering is not sufficiently tempered, the strength becomes too high, and the aperture is extremely lowered. Therefore, T2 is set to 350 ° C. or higher. On the other hand, when the T2 exceeds 550 ° C., it becomes difficult to achieve a tensile strength of 1900 MPa or more. Therefore, T2 is set to 550 ° C. or lower.
- the optimum range of the tempering heating temperature (T2) can be appropriately determined in the range of 350 to 550 ° C. according to the required strength.
- the t2 is preferably 70 seconds or less, more preferably 50 seconds or less, still more preferably 40 seconds or less, and even more preferably 12 seconds or less.
- the present invention is based on the premise that high-frequency heating is performed. If t2 is too short, hardness variation in the cross section in the circumferential direction is likely to occur in the case of a thick steel wire, and stable strength improvement is achieved. It becomes difficult to plan. Therefore, in the present invention, t2 is set to 5 seconds or more. The t2 is preferably 7 seconds or longer, more preferably 10 seconds or longer.
- the said average cooling rate (said CR2) shall be 30 degrees C / s or more.
- the CR2 is preferably 40 ° C./s or more, more preferably 50 ° C./s or more.
- the upper limit of CR2 is about 300 ° C./s.
- the cooling method includes water cooling, mist cooling and the like. Moreover, the average cooling rate from 100 degreeC to room temperature is not specifically limited.
- the steel wire for springs of the present invention satisfying the above component composition / structure has a tensile strength of 1900 MPa or more and a drawing measured by a tensile test described later of 45% or more.
- the drawing required by this tensile test is one of the indexes representing the ductility of the material. The higher the aperture, the higher the ductility and the less likely to break during spring forming, and the better the coiling property.
- the steel wire for springs of the present invention is suitable as a steel wire for cold forming springs (particularly, a steel wire for suspension springs) because it has high strength, excellent coiling properties and hydrogen brittleness resistance as described above.
- a coil spring for example, a valve spring or a suspension spring used for an engine, a suspension, etc.
- high strength and excellent hydrogen brittleness resistance can be realized.
- the above quenching was performed as follows. That is, it was heated from 100 ° C. to the quenching heating temperature (T1) shown in Tables 3 and 4 at an average temperature increase rate (HR1) shown in Tables 3 and 4, and held at T1 (holding time (t1) is As shown in Table 3 and Table 4). Thereafter, in all of the examples, spray cooling was performed from the heating temperature (T1) to 300 ° C. to cool at 50 ° C./s or more, and from 300 ° C. to 80 ° C., the averages shown in Table 3 and Table 4, respectively. Cooling was performed at a cooling rate (CR1). The cooling from 300 ° C. to 80 ° C. was performed by spray cooling, immersion in a water tank, or cooling using He gas in some examples (experimental scale). The temperature was allowed to cool from 80 ° C. to room temperature.
- tempering was performed as follows. That is, the sample was heated from 100 ° C. to a temperature range (T2) of 350 to 550 ° C. at the average heating rate (HR2) shown in Tables 3 and 4 and held at T2 (holding time (t2) is shown in Table 3). And as shown in Table 4). Then, it cooled from the said T2 (however, when T2 is 400 degreeC or more) to 100 degreeC by the average cooling rate (CR2) shown in Table 3 and Table 4. This cooling was performed by spray cooling. In addition, it was left to cool from 100 ° C. to room temperature. In Table 4, No. 45-69 and no. Since the tempering heating temperature (T2) was changed from 70 to 94, spring steel wires having different strengths and the like were obtained as shown in Table 6 below.
- evaluation of steel structure evaluation of retained austenite amount and prior austenite grain size number
- evaluation of tensile properties evaluation of tensile strength and drawing
- evaluation of hydrogen embrittlement resistance by the following methods Went.
- the amount of residual ⁇ determined by the X-ray diffraction is calculated as a volume ratio, but the value of the volume ratio can be read as an area ratio as it is. Therefore, in the present invention, the unit of the residual ⁇ amount is treated as an area ratio.
- Tables 1 to 6 can be considered as follows (the following numbers indicate the example numbers in Tables 3 to 6). That is, no. 1 to 4, 6, 7, 11 to 16, 18 to 21, 25, 26, 28, 29, 33 to 35, 37, 38, 41, and 45 to 94 satisfy the requirements defined in the present invention. It has high strength and excellent coiling and hydrogen embrittlement resistance.
- No. No. 9 has an excessive amount of P.
- No. 10 has an excessive amount of S.
- No. 17 had an excessive amount of Nb, so that the aperture was small and the coiling property was lowered.
- No. 22 to 24, 27, 30 to 32, 36, 39, 40, and 42 to 44 are examples in which steel materials having the specified component composition are used, but quenching and tempering were not performed under the specified conditions in the manufacturing process. is there. In these examples, the prescribed structure was not obtained, and as a result, the coiling property and the hydrogen embrittlement resistance deteriorated. Details are as follows.
- No. 30 to 32 are examples of quenching under general conditions, but because the average cooling rate (CR1) during quenching is too fast, a specified amount of retained austenite cannot be secured, and coiling and hydrogen embrittlement resistance. At least one has deteriorated.
- CR1 average cooling rate
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Abstract
Description
(a)Cu:0.05~1.5%、およびNi:0.05~1.5%よりなる群から選択される1種以上の元素;
(b)Ti:0.10%以下(0%を含まない)、B:0.010%以下(0%を含まない)、Nb:0.10%以下(0%を含まない)、Mo:0.5%以下(0%を含まない)、およびV:0.3%以下(0%を含まない)よりなる群から選択される1種以上の元素;
・100℃から下記焼入れ加熱温度(T1)までの平均昇温速度(HR1):40℃/s以上
・焼入れ加熱温度(T1):850~1000℃
・焼入れ加熱温度での保持時間(t1):90秒以下
・焼入れ加熱後の300℃から80℃までの平均冷却速度(CR1):5~30℃/s
(焼戻し条件)
・100℃から下記焼戻し加熱温度(T2)までの平均昇温速度(HR2):30℃/s以上
・焼戻し加熱温度(T2):350~550℃
・焼戻し加熱温度での保持時間(t2):5~90秒
・焼戻し加熱後の、上記T2(但し、上記T2が400℃以上の場合は400℃)から100℃までの平均冷却速度(CR2):30℃/s以上
〔残留オーステナイト(残留γ)量:6~15面積%〕
オーステナイトは、柔らかく、本質的に延性の高い相である。従って、硬質なマルテンサイト中に残留オーステナイトを適度に分散させることによって、絞りが向上し、良好なコイリング性を確保できる。更に残留オーステナイトは、水素トラップサイトとして有効に作用するため、水素脆化に対する感受性を低減させて耐水素脆性の向上にも寄与する。本発明では、優れたコイリング性と耐水素脆性の両特性を確保するため、残留オーステナイト量を6面積%以上とした。残留オーステナイト量は、好ましくは8面積%以上、より好ましくは10面積%以上である。
旧オーステナイト結晶粒の微細化によってコイリング性と耐水素脆性が向上する。そのため、本発明では、JIS G 0551に規定の方法で求められる旧オーステナイト(旧γ)結晶粒度番号を10.0番以上とした。該旧γ結晶粒度番号は、好ましくは10.5番以上、より好ましくは11.0番以上である。尚、前記旧γ結晶粒度番号の上限は14.0番程度である。
本発明の鋼材(鋼線)は、組織が、焼戻しマルテンサイト主体(全組織に占める割合で70面積%以上)である。高強度かつ高靭性を確保するため、後述する焼入れ焼戻し処理を行って、上記焼戻しマルテンサイト主体の組織とする必要がある。焼戻しマルテンサイトは、好ましくは80面積%以上である。
Cは、高強度を確保するのに必要な元素であり、また微細な炭化物形成により耐水素脆性を向上させるのに有効な元素でもある。そのためCを0.40%以上含有させる。C量は、好ましくは0.50%以上、より好ましくは0.58%以上である。しかしC量が過剰になると、焼入れ焼戻し後の残留オーステナイト量が必要以上に増加し、耐水素脆性がかえって低下する場合がある。またCは、耐食性を劣化させる元素でもあるため、最終製品であるばね製品(懸架ばね等)の腐食疲労特性を高めるにはC量を抑える必要がある。よって本発明では、C量を0.65%以下とした。C量は、好ましくは0.62%以下である。
Siは、強度を確保するのに必要な元素であると共に、炭化物を微細にする効果がある。こうした効果を有効に発揮させるためには、Siを1.0%以上含有させる必要がある。Si量は、好ましくは1.3%以上、より好ましくは1.8%以上である。一方、Siは脱炭を促進させる元素でもある。過度にSiが含まれていると、鋼線の製造工程において、鋼材表面の脱炭層形成が促進される。その結果、該脱炭層の削除のためにピーリング工程が必要となり、製造コストの増加を招く。よって、本発明ではSi量の上限を3.0%とした。Si量は、好ましくは2.5%以下、より好ましくは2.2%以下である。
Mnは、脱酸元素として利用されると共に、鋼中の有害元素であるSとMnSを形成してSの無害化に有益な元素である。また、強度向上に寄与する元素でもある。これらの効果を有効に発揮させるため、Mn量を0.6%以上とする。Mn量は、好ましくは0.7%以上、より好ましくは0.8%以上である。しかしMnが過剰に含まれると、残留γ量が必要以上に増加しやすくなり、耐水素脆性や延性(コイリング性)がかえって低下する。これらの理由から、本発明ではMn量を2.0%以下とする。Mn量は、好ましくは1.6%以下、より好ましくは1.3%以下である。
Pは、鋼材の延性(コイリング性)を劣化させる有害元素である。よってP量は低い方が望ましく、その上限を0.015%とする。P量は、好ましくは0.010%以下、より好ましくは0.008%以下である。
Sも、上記Pと同様に鋼材の延性(コイリング性)を劣化させる有害元素である。よってS量は低い方が望ましく、その上限を0.015%とする。S量は、好ましくは0.010%以下、より好ましくは0.008%以下である。
Alは、主に脱酸元素として添加される。また、NとAlNを形成して固溶Nを無害化すると共に組織の微細化にも寄与する。これらの効果を十分に発揮させるには、Al量を0.001%以上とする必要がある。Al量は、好ましくは0.002%以上である。しかし、AlはSiと同様に脱炭を促進させる元素でもある。よって、Siを多く含有するばね用鋼線ではAl量を抑える必要があり、本発明ではAl量を0.10%以下とした。Al量は、好ましくは0.07%以下、より好ましくは0.030%以下、更に好ましくは0.020%以下である。
Cuは、表層脱炭の抑制や耐食性の向上に有効な元素である。この様な効果を発揮させるには、Cu量を0.05%以上とすることが好ましく、より好ましくは0.2%以上である。しかしCuが過度に含まれると、熱間加工時に割れが発生したり、焼入れ後の残留オーステナイト量が極端に増えて、鋼材の延性が劣化する場合がある。よって、本発明ではCu量を1.5%以下とすることが好ましい。Cu量は、より好ましくは1.3%以下、更に好ましくは0.7%以下、より更に好ましくは0.4%以下である。尚、Cu量が0.5%を超える場合には、Cuと同量またはそれ以上のNiを存在させる[Ni量(質量%)≧Cu量(質量%)]ことによってCuによる熱間脆性を抑制できる。
Tiは、Sと硫化物を形成してSの無害化を図るのに有用な元素である。またTiは炭窒化物を形成して組織を微細化する効果も有する。これらの効果を発揮させるには、0.02%以上のTiを含有させることが好ましい。Ti量は、より好ましくは0.05%以上である。しかしTi量が過剰になると、粗大なTi硫化物が形成され延性が劣化する場合がある。よって本発明では、Ti量を0.10%以下とすることが好ましい。コスト低減の観点からはTi量を0.07%以下に抑えることがより好ましい。
本発明のばね用鋼線の上記組織を容易に確保するには、例えば鋼材を溶製後、圧延して線材を得た後に伸線加工を施し、次いで焼入れ焼戻し処理する工程において、該焼入れ焼戻し処理を下記要領で行う必要がある。
(100℃から焼入れ加熱温度(T1)までの平均昇温速度(HR1):40℃/s以上)
100℃から焼入れ加熱温度(T1)までの平均昇温速度(HR1)が40℃/sよりも遅いと、旧オーステナイト結晶粒が粗大化し、特性(コイリング性および耐水素脆性)が低下する。よって、上記HR1を40℃/s以上とする。上記HR1は、好ましくは50℃/s以上、より好ましくは100℃/s以上である。一方、上記HR1の上限は、温度制御の観点から400℃/s程度である。
焼入れ加熱温度(T1)が1000℃よりも高いと、旧オーステナイト結晶粒が粗大化し、特性(コイリング性および耐水素脆性)が低下する。よって前記T1を1000℃以下とする。前記T1は、好ましくは980℃以下、より好ましくは930℃以下である。一方、前記T1が850℃よりも低いと、炭化物が十分に固溶せず、オーステナイト化を十分図ることができない。その結果、この焼入れ焼戻し工程で、焼戻しマルテンサイト組織を十分確保できず、高強度が得られない。よって前記T1は850℃以上とする。前記T1は、好ましくは870℃以上、より好ましくは900℃以上である。
焼入れ加熱温度(T1)での保持時間(t1)が90秒よりも長いと、旧オーステナイト結晶粒が粗大化し、特性(コイリング性および耐水素脆性)が低下する。よって前記t1は90秒以下とする。前記t1は、好ましくは60秒以下、より好ましくは40秒以下である。
焼入れ加熱後の300℃から80℃までの平均冷却速度(CR1)が30℃/sよりも速いと、マルテンサイト変態が進行し、焼戻し後の残留オーステナイト量が規定範囲の下限値を下回る。よって本発明では、前記CR1を30℃/s以下とする。前記CR1は、好ましくは25℃/s以下、より好ましくは20℃/s以下である。一方、前記CR1が小さすぎると、残留オーステナイト量が規定範囲の上限を上回り、上述した通りコイリング性や耐水素脆性の低下を招く。よって本発明では、前記CR1を5℃/s以上とする。前記CR1は、好ましくは10℃/s以上、より好ましくは15℃/s以上である。
(100℃から焼戻し加熱温度(T2)までの平均昇温速度(HR2):30℃/s以上)
上記平均昇温速度(HR2)が遅いと、残留オーステナイトが分解し、減少して、規定量の残留オーステナイトを確保できない。よって本発明では、上記HR2を30℃/s以上とする。前記HR2は、好ましくは40℃/s以上、より好ましくは50℃/s以上である。一方、上記平均昇温速度(HR2)が速すぎると、温度制御が困難になり強度バラツキが生じ易くなる。よって前記HR2は、好ましくは300℃/s以下であり、より好ましくは200℃/s以下である。
焼戻し加熱温度(T2)が低すぎると、十分焼戻されず、強度が高くなりすぎて、絞りが極端に低下するといった不具合が生じる。よって、前記T2は350℃以上とする。一方、前記T2が550℃を超えると、引張強度1900MPa以上を達成することが困難となる。よって前記T2は550℃以下とする。焼戻し加熱温度(前記T2)の最適範囲は、350~550℃の範囲内で要求強度に応じて適宜決定することができる。
焼戻し加熱温度(T2)での保持時間(t2)が90秒よりも長いと、残留γが分解し、規定量の残留γが得られない。前記t2は、好ましくは70秒以下、より好ましくは50秒以下、更に好ましくは40秒以下、より更に好ましくは12秒以下である。一方、本発明は高周波加熱を行うことを前提とするものであり、前記t2が短すぎると、太径鋼線の場合、円周方向の断面内の硬さバラツキが生じ易く、安定した強度向上を図ることが困難となる。よって本発明では、前記t2は5秒以上とする。前記t2は、好ましくは7秒以上、より好ましくは10秒以上である。
焼戻し加熱後の、上記T2(但し、上記T2が400℃以上の場合は400℃)から100℃までの平均冷却速度(CR2)が遅いと、残留オーステナイトが分解、減少し、規定量の残留オーステナイトを確保できない。よって本発明では、上記平均冷却速度(前記CR2)を30℃/s以上とする。前記CR2は、好ましくは40℃/s以上、より好ましくは50℃/s以上である。尚、前記CR2の上限は300℃/s程度である。
(残留オーステナイト量の測定)
残留オーステナイト量は、X線回折で測定した。分析装置は、株式会社リガク製 2次元微小部X線回折装置 RINT-RAPIDIIを用い、スポット径は直径300μmとした。α-Feのピーク強度(110)とγ-Feのピーク強度(200)から、残留オーステナイト量(残留γ量)を求めた。
鋼線の横断面(ばね用鋼線の中心軸に垂直な断面)のD(直径)/4位置が観察面となるように試料を採取した。この採取した試料を樹脂に埋め込み、研磨後にピクリン酸系の腐食液を用いて旧オーステナイト結晶粒界を現出させ、JIS G 0551に規定の方法で旧オーステナイト結晶粒度番号を求めた。
得られた鋼線を用い、JIS14号試験片に加工した。該試験片を用い、JIS Z 2241に従って、万能試験機にてクロスヘッドスピード10mm/minの条件で引張試験を行って、TS(引張強度)と絞りを測定した。そして、引張強度が1900MPa以上を高強度であると評価した。また、絞りが45%以上のものを、コイリング性に優れると評価した。
鋼線から幅10mm×厚さ1.5mm×長さ65mmの試験片を切り出した。該試験片に対して4点曲げにより1400MPaの応力を作用させた状態で、該試験片を硫酸(0.5mol/L)とチオシアン酸カリウム(0.01mol/L)の混合溶液に浸漬させた。そして、ポテンションスタットを用いてSCE電極よりも卑な-700mVの電圧をかけ、割れが発生するまでの時間(破断時間)を測定した。該破断時間が700秒(sec)以上の場合を耐水素脆性に優れると評価した。
Claims (5)
- C:0.40~0.65%(質量%の意味、化学成分について以下同じ)、
Si:1.0~3.0%、
Mn:0.6~2.0%、
P:0.015%以下(0%を含まない)、
S:0.015%以下(0%を含まない)、および
Al:0.001~0.10%
を満たし、残部が鉄及び不可避不純物からなり、
全組織に対し、
焼戻しマルテンサイト:70面積%以上、および
残留オーステナイト:6~15面積%を満たすと共に、
JIS G 0551に規定の方法で求められる旧オーステナイト結晶粒度番号が10.0番以上であり、かつ、
引張強度が1900MPa以上であることを特徴とするコイリング性と耐水素脆性に優れた高強度ばね用鋼線。 - 更に、Cu:0.05~1.5%、およびNi:0.05~1.5%よりなる群から選択される1種以上の元素を含む請求項1に記載の高強度ばね用鋼線。
- 更に、
Ti:0.10%以下(0%を含まない)、
B:0.010%以下(0%を含まない)、
Nb:0.10%以下(0%を含まない)、
Mo:0.5%以下(0%を含まない)、および
V:0.3%以下(0%を含まない)
よりなる群から選択される1種以上の元素を含む請求項1に記載の高強度ばね用鋼線。 - 請求項1~3のいずれかに記載の高強度ばね用鋼線を用いて得られたばね。
- 請求項1~3のいずれかに記載の高強度ばね用鋼線を製造する方法であって、
請求項1~3のいずれかに記載の成分組成を満たす鋼材を用い、伸線後に行う焼入れ焼戻しを、下記の焼入れ条件および焼戻し条件の全てを満たすように行うことを特徴とするコイリング性と耐水素脆性に優れた高強度ばね用鋼線の製造方法。
(焼入れ条件)
・100℃から下記焼入れ加熱温度(T1)までの平均昇温速度(HR1):40℃/s以上
・焼入れ加熱温度(T1):850~1000℃
・焼入れ加熱温度での保持時間(t1):90秒以下
・焼入れ加熱後の300℃から80℃までの平均冷却速度(CR1):5~30℃/s
(焼戻し条件)
・100℃から下記焼戻し加熱温度(T2)までの平均昇温速度(HR2):30℃/s以上
・焼戻し加熱温度(T2):350~550℃
・焼戻し加熱温度での保持時間(t2):5~90秒
・焼戻し加熱後の、上記T2(但し、上記T2が400℃以上の場合は400℃)から100℃までの平均冷却速度(CR2):30℃/s以上
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EP (1) | EP2857540A4 (ja) |
JP (1) | JP5364859B1 (ja) |
KR (1) | KR20150002848A (ja) |
CN (1) | CN104321454B (ja) |
MX (1) | MX2014014448A (ja) |
TW (1) | TWI496924B (ja) |
WO (1) | WO2013179934A1 (ja) |
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WO2015129403A1 (ja) * | 2014-02-28 | 2015-09-03 | 株式会社神戸製鋼所 | 高強度ばね用圧延材および高強度ばね用ワイヤ |
WO2017122827A1 (ja) * | 2016-01-15 | 2017-07-20 | 株式会社神戸製鋼所 | 高強度ばね用ワイヤおよびその製造方法 |
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- 2013-05-20 CN CN201380025097.5A patent/CN104321454B/zh not_active Expired - Fee Related
- 2013-05-20 WO PCT/JP2013/063934 patent/WO2013179934A1/ja active Application Filing
- 2013-05-20 MX MX2014014448A patent/MX2014014448A/es unknown
- 2013-05-20 EP EP13797230.3A patent/EP2857540A4/en not_active Withdrawn
- 2013-05-20 US US14/397,734 patent/US20150101715A1/en not_active Abandoned
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EP2857540A4 (en) | 2016-03-02 |
KR20150002848A (ko) | 2015-01-07 |
EP2857540A1 (en) | 2015-04-08 |
TW201408802A (zh) | 2014-03-01 |
CN104321454A (zh) | 2015-01-28 |
MX2014014448A (es) | 2015-08-05 |
JP5364859B1 (ja) | 2013-12-11 |
TWI496924B (zh) | 2015-08-21 |
US20150101715A1 (en) | 2015-04-16 |
JP2014005532A (ja) | 2014-01-16 |
CN104321454B (zh) | 2016-08-17 |
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