CN1966755B - Steel wire material for spring with excellent acid rinsing property - Google Patents
Steel wire material for spring with excellent acid rinsing property Download PDFInfo
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- CN1966755B CN1966755B CN2006101603482A CN200610160348A CN1966755B CN 1966755 B CN1966755 B CN 1966755B CN 2006101603482 A CN2006101603482 A CN 2006101603482A CN 200610160348 A CN200610160348 A CN 200610160348A CN 1966755 B CN1966755 B CN 1966755B
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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
- C22C38/34—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
- C22C38/002—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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
- C22C38/24—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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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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
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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
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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
- F16F1/04—Wound springs
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Abstract
The steel wire material for spring in accordance with the present invention comprises, on the percent by mass basis, C: 0.35 to 0.7%, Si: 1.4-2.5%, Mn: 0.05-1.0%, Cr: 0.5-1.9%, P: less than 0.02% (not including 0%), and S: less than 0.02% (not including 0%), wherein the concentration difference of Cr between on the surface and in the steel is less than 2.50%. Plenty of steel wire materials containing Si and Cr have excellent acid rinsing property even without additional alloy components containing necessary component such as Mo and the like.
Description
Technical field
The present invention relates to a kind of steel wire material for spring of pickling excellence, in detail, just relating to Si and Cr is the steel wire material for spring that alloying element contains in a large number.Steel wire material for spring of the present invention is applicable to bearing spring of the valve spring that uses and clutch spring, brake spring, stabilizer, torsion bar etc. etc. on engines such as automobile.
Background technology
The chemical ingredients that is used for the spring steel of valve spring and bearing spring etc. for example is defined as JIS G3565～JIS G 4801 etc., adopts suitable steel grade according to the kind of spring design etc.Recently, along with the reductionization of waste gas and oil consumption, the miniaturization and of spring is advanced, and the design stress of spring also improves, for example, expectation can provide the tensile strength of spring precursor (Q-tempering processing material) can realize being approximately the above high-intensity steel wire material for spring of 1600MPa.In addition,, also expect the raising of yield-point, have use can improve the tendency of the Si and the steel wire material that Cr contains in a large number as alloying element of yield-point by solution strengthening in order to improve as the weather resistance under the atmosphere of one of important characteristic of spring.
In general, its manufacturing of spring is the heating steel billet, the wire rod (rolled wire) of hot rolling is applied lubricant to the surface as required and carries out after epithelium handles (surperficial epithelium processing), carries out drawing, processing (thermoforming or cold shaping) the line footpath up to regulation.Because heating is normally carried out under oxidizing atmosphere, so on the surface of rolled wire, can generate the zone of oxidation of the Fe oxide compound that is called as " expanded skin " or " oxide skin ".If use this rolled wire be attached with oxide skin to make spring, surface spots etc. then can take place and cause the reduction of quality, therefore before carrying out drawing and handling, be used for removing the cleanup acid treatment of descaling.
Fig. 1 represents to adopt the Fe-SEM device to observe the photo in the cross section of the rolled wire that surface attachment at the steel that contains Si and Cr in a large number (high Si is high, and Cr contains steel) has oxide skin.This is equivalent to the No.E-1 of embodiment described later.As shown in Figure 1, oxide skin is made of following successively from the top layer side: rhombohedral iron ore (hematite) (Fe
2O
3), magnetite (magnetite) (Fe
3O
4), wustite (wustite) (FeO), fayalite (fayalite) (2FeOSiO2).Between steel (ferrite) and oxide skin, also generate the internal layer oxide skin (subscale) that Si and denseization of Cr are arranged, also generate grain boundary oxidation layer based on the Cr oxide compound.
Wherein, fayalite is the low-melting oxide compound that occurs when using the steel that contains Si in a large number, is the difficult separability material that is difficult to peel off in common cleanup acid treatment.For example, if the high Cr of high Si is contained more than the eutectic temperature (about 1170 ℃) that steel is heated to fayalite and wustite, then their oxide compound intricately complexing forms fine and close melting layer, in addition, if be heated to more than 1200 ℃, then above-mentioned fusion mutually and have Cr to invade in the fayalite, with ferritic interface on denseization and make grain boundary oxidation layer (details aftermentioned) formation.Remove by operation thereafter in case so, the Cr of denseization is extremely difficult.
In addition, known have internal layer oxide skin that the ferritic sensitization through cleanup acid treatment is reduced, and causes the reduction of pickling.If the pickling reduction then after cleanup acid treatment, because residual based on the expanded skin of internal layer oxide skin, so reduce with the tack that puts on surperficial lubricant (being used for surperficial epithelium handles), probably can be processed interrupt line in drawing.Even can not cause broken string, also can in drawing processing, crack (be full of cracks), in being shaped (cold coiling cold coiling), spring loses.These problems, for example, can be by prolonging the cleanup acid treatment time, remove expanded skin fully and reduce, but, because the soak time in the acid solution is elongated,, acid causes the deterioration of top layer smooth finish so becoming violent to ferritic erosion (attack), finally also will damage the weather resistance under atmosphere.In addition,, cause the embrittlement (hydrogen embrittlement) of steel so hydrogen occlusion amount increases when ferrite is corroded, in drawing processing, the situation that causes broken string is arranged because the part of the hydrogen that acid takes place can be diffused in the steel rapidly and be absorbed.
The grain boundary oxidation layer appears under the situation of steel that use contains Cr in a large number.This is that if aerobic immerses in hot rolling, then the oxidation rate compared with the intragranular crystal boundary can become big because the avidity of Cr and oxygen is very strong.If grain boundary oxidation is to a certain degree to advance, then when spring was shaped, spring can damage owing to otch (notch) effect that grain boundary oxidation portion brings.In general, the grain boundary oxidation layer has thickness along with internal layer oxide skin thick more and become thick more tendency.
So, if use the steel wire material for spring that contains Si and Cr in steel in a large number, the then pickling reduction owing to aforesaid various reasons has the fatigue characteristic of spring to reduce such problem.
In order to solve the above problems, for example, open in the flat 6-299295 communique the spy, disclose by adding the alloying element of Mo etc., and Heating temperature and rolling end temp during the control hot rolling, and with the method for film thickness monitoring below 10 μ m of oxide skin.
Yet, in aforesaid method, except Cr and Si, as must adding the alloying element of the high price of Mo etc. by composition.
Summary of the invention
The present invention In view of the foregoing carries out, and its purpose is, a kind of steel wire material for spring is provided, and in the steel wire material for spring that contains Si and Cr in a large number, even do not add alloying constituent as Mo that must composition etc., its pickling is also very excellent.
The steel wire material for spring of the present invention that can solve above-mentioned problem contains: the C:0.35～0.7% (meaning of quality %.Below do not have the special suggestion promptly identical), Si:1.4～2.5%, Mn:0.05～1.0%, Cr:0.5～1.9%, P:0.02% following (not containing 0%), and S:0.02% following (not containing 0%), the Cr concentration on top layer and the difference of the Cr concentration in the steel are below 2.50%.
In preferred embodiment, also contain from the group of following formation, select at least a: V:0.07～0.4%, Ti:0.01～0.1% and Nb:0.01～0.1%.
In preferred embodiment, also contain Ni:0.15～0.8%.
Can solve the spring of the present invention of above-mentioned problem, use any one above-mentioned steel wire material for spring and can access.
Steel wire material for spring of the present invention is except the concentration of the Cr of skin section significantly is suppressed, because the thickness of oxide skin, internal layer oxide skin and grain boundary oxidation layer is all extremely thin, so the pickling excellence.If adopt steel wire material for spring of the present invention to make spring, then can provide a kind of spring, it just can easily peel off oxide skin and internal layer oxide skin by pickling process, so the surface texture excellence, and fatigue characteristic are also high.
Description of drawings
Fig. 1 is a Fe-SEM photo of observing the cross section of the rolled wire that is attached with oxide skin.
Fig. 2 is in order to measure the Cr concentration on top layer, the figure for the examination material of regulation is measured in quantitative analysis according to the EPMA line, Fig. 2 (a) is that expression is about Fe, X ray intensity (cps) and figure from the relation of the distance of skin section, Fig. 2 (b) is an expression Cr concentration (%) and figure from the relation of the distance of skin section.
Embodiment
The present inventor has carried out research with keen determination for the pickling that improves the steel wire material for spring that contains Si and Cr in a large number.Its result such as back describe in detail, if point out particularly suitably to control hot rolling preceding heating process and soaking operation, then denseization of Cr of wire surface (particularly denseization of Cr in fayalite) is suppressed, the Cr concentration on top layer and the Cr concentration in the steel poor (below, the situation that simply is designated as Δ Cr is arranged) significantly reduced, therefore improve in pickling personality other places, thereby finish the present invention.
Below describe the present invention in detail.
As described above, steel wire material for spring of the present invention contains: C:0.35～0.7%, Si:1.40～2.5%, Mn:0.05～1.0%, Cr:0.50～1.9%, P:0.02% following (not containing 0%), and S:0.02% is following, surplus: Fe and unavoidable impurities, wherein, poor (the Δ Cr) of Biao Mian Cr concentration and the Cr concentration in the steel is below 2.50%.
In this manual, so-called " steel wire material " meaning is behind the heating steel billet, is hot rolled into the steel (rolled stock) of wire, is to implement cleanup acid treatment material before.
At first, be illustrated with regard to composition in the steel.
C：0.35～0.7％
C is the raising that helps the intensity (hardness) behind the Q-tempering, and improves the element of atmosphere weather resistance.Be lower than at 0.35% o'clock in C amount, can not bring into play above-mentioned effect effectively, on the other hand, if surpass 0.7%, toughness deteriorated ductility then, be full of cracks becomes and is easy to propagate weather resistance and reduces.In addition, be applied in the spring of cold coiling as valve spring etc., because toughness ductile deterioration, having with the surface spots is the situation of losing generation of basic point.The C amount is preferably more than 0.51%, below 0.61%.
Si：1.4～2.5％
Si helps intensity to improve as the solution strengthening element, also is the element that can improve yield-point.When Si was lower than 1.4, substrate intensity was insufficient.But, if Si becomes excessive above 2.5%, then through surpassing A
3The thermal treatment of transformation temperature has the ferrite decarburization to produce easily on the surface, the solution strengthening effect can't be brought into play effectively.Si is preferably more than 1.7%, below 2.1%.
Mn：0.05～1.0％
Mn is the element that improves the hardenability in the steel.In order to bring into play this effect effectively, the addition of Mn is more than 0.05%.But if Mn amount surpasses 1.0% and by excessive interpolation, then hardenability increased cold tissue and becomes and generate drawing processibility deterioration easily.In addition, " spring operation (c) " as described later after hot rolling before the cleanup acid treatment, when carrying out being the purpose annealing operation with wire rod softening, can't avoid expensive.Mn is preferably more than 0.4%, below 0.9%.
Cr：0.5～1.9％
Cr is an element of strengthening the base material of wire rod by solution strengthening.In addition, equally also playing a part hardenability effectively with Mn improves.In order to bring into play such effect effectively, add the Cr more than 0.5%.But,, then when rolling postcooling, had cold tissue to generate drawing processibility deterioration easily if Cr surpasses 1.9%.Cr is preferably more than 0.6%, below 1.75%.
P:0.02% following (not containing 0%)
P makes embrittlement of grain boundaries in old austenite grain boundary segregation, and fatigue characteristic are reduced, and is therefore preferably the least possible.In the present invention, from industrial production its upper limit is made as 0.02%.
S:0.02% following (not containing 0%)
S makes embrittlement of grain boundaries in old austenite grain boundary segregation, and fatigue characteristic are reduced, and is therefore few more good more.In the present invention, from industrial production its upper limit is made as 0.02%.
Steel wire material for spring of the present invention contains mentioned component, and surplus is iron and unavoidable impurities.
In the present invention, for the purpose that further improves hydrogen embrittlement resistance, preferably also contain from the group of following formation, select at least a: V:0.07～0.4%, Ti:0.01～0.1% and Nb:0.01～0.1%.In addition, the flexible purpose for behind the raising Q-tempering preferably contains Ni.Below described in detail with regard to each element.
V：0.07～0.4％
V-arrangement becomes fine carbide and nitride, is the element that helps the raising of hydrogen embrittlement resistance.In addition, also can improve fatigue characteristic.In addition, because the effect of crystal grain miniaturization and toughness and yield-point improve, also help the go down raising of drag of elastic force.In order to make such effect performance effectively, preferably add the V more than 0.07%.But, if excessively add V, then when quenching heating, in austenite, there is not the carbide amount of solid solution to increase above 0.4%, except can not get full intensity and hardness, the retained austenite amount also increases, and spring hardness reduces.V more preferably more than 0.1, below 0.35%.
Ti：0.01～0.1％
Ti makes the old austenite crystal grain miniaturization behind the Q-tempering, is the element that helps the raising of hydrogen embrittlement resistance.In addition, also has atmosphere weather resistance raising effect.In order to bring into play such effect effectively, preferably add the Ti more than 0.01%.But if excessively add Ti, then thick nitride will be separated out easily, and the atmosphere weather resistance reduces, therefore preferably with its upper limit as 0.1%.Ti more preferably more than 0.04%, below 0.085%.
Nb：0.01～0.1％
Nb forms the fine precipitate of being made up of carbide, nitride, sulfide and their complex chemical compound, is the element that helps the raising of hydrogen embrittlement resistance.In addition, because the crystal grain micronized effect also can improve toughness and yield-point.In order to bring into play such effect effectively, preferably add the Nb more than 0.01%.But, if surpass 0.1% and excessively add Nb, then when quenching heating, in the austenite not the carbide amount of solid solution increase the tensile strength that can not get stipulating.In addition, the fatigue that the nitride of thickization causes taking place easily loses.Nb more preferably more than 0.02%, below 0.05%.
Ni：0.15～0.8％
Ni is the flexible element behind the raising Q-tempering.In addition, to the rolling middle ferrite decarburization that produces restraining effect being arranged also before rolling.In order to bring into play such effect effectively, and add the Ni more than 0.15%.But if Ni surpasses 0.8%, then hardenability increases, and generates cold tissue easily after rolling.In addition, the retained austenite amount also increases, and spring hardness reduces.Ni is preferably more than 0.25%, below 0.55%.
More than, composition in the steel among the present invention has been described.
Poor (the Δ Cr) of the Cr concentration on top layer and the Cr concentration in the steel: below 2.50%
Steel wire material for spring of the present invention, Δ Cr are suppressed very lowly, are below 2.50%.Shown in the embodiment, uprise as described later as if Δ Cr, then pickling reduction, but this is owing to there is CrO (OH) to generate in pickle solution, produces the passive film of Cr on the ferrite surface.In the present invention, describe in detail as described later, particularly because suitably control hot rolling preceding heating process and soaking operation, so suppress Δ Cr very low.Δ Cr is few more good more, for example is preferably below 2.0%, more preferably below 1.5%.Its lower limit is not particularly limited, if consider the actual job level, then is preferably more than 0.4%.
Here, adopt the measuring method of Fig. 2 explanation " the Cr concentration on top layer ".Fig. 2 is the confession examination material that adopts following making, from the scope of skin section to the center of inside 0.3mm, the figure that measures according to the EPMA line quantitative analysis of following condition, the X ray intensity (cps) of Fig. 2 (a) expression Fe and relation from the distance of skin section, Fig. 2 (b) expression Cr concentration and relation from the distance of skin section.Shown in Fig. 2 (a), place when the X ray intensity of Fe is reached maximum value is as ferrite interface (oxide skin and ferritic border), with this zone definitions is " skin section ", and the maximum value of the Cr amount in this skin section is defined as " the Cr concentration on top layer " (with reference to Fig. 2 (b)).Above-mentioned " top layer " part, also different according to creating conditions of composition in the steel and wire rod etc., but contain fayalite to I haven't seen you for ages.
EPMA determinator: use NEC system X-ray microanalyzer (microanalyzer) " JXA-8800 RL "
For trying material: this steel that will be attached with oxide skin are imbedded resin, to after carrying out mirror ultrafinish perpendicular to the cross section (mensuration face) of rolling direction, adopt osmium (osmium) to carry out evaporation with abrasive in order to keep electroconductibility.
Acceleration voltage: 15kV
Irradiation electric current: 0.3 μ A
Quantitative line analysis: the interval 1 μ m of distribution, measure total 300 points
More than Δ Cr explanation the present invention of just tool feature.
Steel wire material for spring of the present invention, as shown below, the preferred suitably thickness of controlled oxidation skin and the thickness of composition and internal layer oxide skin, in view of the above, pickling further improves.
(thickness of oxide skin)
The thickness of oxide skin is preferably below the 40 μ m.As following detailed description, peel off if consider the oxide skin that the be full of cracks (crackle) that takes place causes in oxide skin, then the thickness of oxide skin more preferably roughly 5 μ m above, below the 25 μ m.
In oxide skin, for example, there is miniature be full of cracks to generate in the process of cooling after rolling and the processing of rolled wire.It is many more that this is considered to be full of cracks, easy more from peeling off of the oxide skin on ferrite surface, so the pickling raising.In general, have the thickness of oxide skin thin more, oxide skin intensity can reduce more, the incidental tendency that chaps, but if the thickness of oxide skin became thin, then because the ductility of oxide skin self increases, internal stress reduces, so be full of cracks tails off.Therefore, the thickness of oxide skin preferably is in the above-mentioned scope.
(composition of oxide skin)
The composition of oxide skin, in volumetric ratio, preferably satisfy following scope haply, fayalite: 2～10% (more preferably 3～7%), wustite 2～20% (more preferably 10～18%), magnetite 35～70% (more preferably 37～50%) and rhombohedral iron ore 20～60% (more preferably 30～55%).According to the present invention, come the controlled oxidation skin to form in the mode that the ratio of the wustite of the few oxide skin separability excellence of ratio of the fayalite of difficult separability and magnetite increases, so pickling further is enhanced.
(thickness of internal layer oxide skin)
The thickness of internal layer oxide skin is preferably below the 2 μ m.In this steel that contain Cr of the present invention, as described above,, (mainly be Cr based on the internal layer oxide skin of Cr at oxide skin and ferritic interface
2O
3) generate, still, because Cr
2O
3In pickling, be varied to CrO (OH), generate the passive film that pickle solution is insoluble, so the pickling reduction.In addition, if passive film generates, then ferritic sensitization reduces, being suppressed of hydrogen, so peeling off of oxide skin need be for a long time.Internal layer oxide skin is got over Bao Yuehao, more preferably below the 8 μ m.
Steel wire material for spring of the present invention, the also preferred thickness of controlling the grain boundary oxidation layer as follows in view of the above, mainly is the fatigue characteristic when improving the shaping spring.
(degree of depth of grain boundary oxidation layer)
The degree of depth of grain boundary oxidation layer (thickness) is preferably below the 10 μ m.The degree of depth of grain boundary oxidation layer is got over Bao Yuehao, more preferably below the 8 μ m.
Also have, grain boundary oxidation such as the above-mentioned steel wire material for spring of being not only also have and are being processed into behind the spring situation that when quenching at austenite region (for example) produces.The concentration that spring is added the grain boundary oxidation layer in man-hour is preferably below the 15 μ m.
More than, steel wire material for spring of the present invention has been described.
Next, the method for making above-mentioned steel wire material for spring is described.
The manufacture method of steel wire material for spring comprises following operation: (a) heating process; (b) the deoxygenated skin operation before the hot-rolled process; (c) hot-rolled process.In the present invention, in order to prevent denseization of Cr, suppress grain boundary oxidation to skin section, to accurately control heat-up rate and Heating temperature in (a) heating process especially, soaking time in (b) the soaking operation and soaking temperature, in view of the above, the Cr concentration of petition of surrender layer significantly.Embodiment as described later, according to the present invention, a kind of spring can be provided, although it uses the steel that contains Si and Cr in a large number, also can significantly suppress denseization of Cr to skin section, the thickness of oxide skin and internal layer oxide skin is also thin, does not also form the grain boundary oxidation layer fully, therefore tensile strength is about more than the 1600MPa excellent in fatigue characteristics.
Below, describe each operation in detail.
(a) heating process
Here, approximately with the heat-up rate more than 10 ℃/minute, be heated to 700 ℃～1000 ℃ temperature.Heat-up rate is lower than under 10 ℃/minute the situation, can not prevent denseization of Cr to skin section effectively.Heat-up rate is preferably more than 15 ℃/minute to be advisable fast.In addition, if Heating temperature surpasses above-mentioned scope, then denseization of Cr propelling, the Cr quantitative change on top layer is many.On the other hand, if Heating temperature is lower than above-mentioned scope, then steel are not fully heated, can not roughing.Heating temperature is preferably more than 750 ℃, below 900 ℃.
(b) soaking operation
Here, with the temperature of roughly 1050 ℃～1250 ℃ (being preferably 1100～1200 ℃), carry out (more preferably 30 minutes～50 minutes) soaking in 20 minutes～60 minutes.The decision of this equal heat condition is in order to prevent denseization of Cr to the top layer, to suppress the carrying out of grain boundary oxidation, for example, soaking temperature and soaking time are if surpass above-mentioned scope, and denseization of Cr is easy to carry out, on the other hand, if soaking temperature and soaking time are lower than above-mentioned scope, then grain boundary oxidation carries out.
In the present invention, the soaking temperature of the Heating temperature of so-called heating process and soaking operation need not be consistent.For example in embodiment described later, high approximately about 50～150 ℃ compared with the Heating temperature soaking temperature, but this is because according to the residence time before the soaking of heating back etc., the temperature during soaking rises.
(c) the deoxygenated skin operation before the hot rolling
Steel wire material for spring of the present invention, need especially to be careful and to make in above-mentioned (a) and operation (b), other operations, the deoxygenated skin operation before (c) hot rolling for example, be not particularly limited with (d) described later hot-rolled process, can suit to select the common condition that is adopted, still, for example recommend control in such a way.
Here, mainly be the oxide skin that contains fayalite in order to remove rapidly, preferably at about 80kgf/mm
2(
785MPa)～160kgf/mm
2(
1569MPa), more preferably at about 100kgf/mm
2(
981MPa)～120kgf/mm
2(
Under hydraulic pressure 1176MPa), carry out about 1 second～10 seconds of high hydraulic pressure shower (shower) (more preferably 3 seconds～7 seconds).Thus, can implement follow-up hot-rolled process apace.When the hydraulic pressure of shower is lower than 80kgf/mm
2The time, the oxide skin thickening probably causes the generation of the engaging-in surface spots that brings in the hot rolling and the increase of top layer Cr concentration.On the other hand, if the hydraulic pressure of shower surpasses 160kgf/mm
2, then the temperature of the briquet before the hot rolling reduces, the rolling difficulty that becomes.
Also have, the deoxygenated skin operation before the hot rolling is not limited to above-mentioned power shower, for example, also can carry out the mechanical removing oxidized scale of shot peening etc.
(d) hot-rolled process
Here, in order to prevent denseization of Cr,, and implement the water-cooled shower of regulation also for the suitable composition of controlled oxidation skin to the fayalite that in hot rolling, generates.
Specifically, in the finish rolling system operation after carry out roughing system, utilize the cooling of shower.The water yield of shower be preferably about 100t/hr above, below the 200t/hr, more preferably 120t/hr above, below the 180t/hr.When the water yield of shower was lower than 100t/hr, the reduction effect of the oxide skin of hope (fayalite) effect of removing and Δ Cr can't be brought into play effectively.On the other hand, if the water yield of shower surpasses 200t/hr, then steel are crossed cold tissue and can be separated out by undercooling.
Finish rolling system temperature mainly be thickness and the composition for suitable controlled oxidation skin, and preferably approximately carries out in the scope of 800 ℃～1000 ℃ (more preferably 950 ℃～980 ℃).
In addition, state identical viewpoint, for example, after preferably finish rolling system being finished, be controlled at 4 ℃/sec～20 ℃/sec (more preferably in the scope of 6 ℃/sec～15 ℃/sec) to the speed of cooling of about 700 ℃ temperature field from catching up with.When the speed of cooling in the said temperature territory is lower than 4 ℃/sec, increases such as scale thickness, pickling reduction.On the other hand, if above-mentioned speed of cooling surpasses 20 ℃/sec, then the hold-time of this temperature field shortens, and the ratio of the wustite that generates at this temperature field reduces, so the pickling reduction.
In the present invention, except above-mentioned steel wire material for spring, also comprise the spring that adopts above-mentioned steel wire material and obtain.According to the present invention, can make a kind of spring, it can not be called as the oxide skin flaw of red oxide skin fully, and surface texture is extremely excellent, and fatigue characteristic are also high.
The method of making spring does not limit especially, can appropriateness adopt used method usually.Representational have, for example, and can be according to making from any of following spring operation (a) to (c).
(a) pickling → surperficial epithelium processing → drawing → Q-tempering (oil tempering (oil temper))
(b) patenting (LP) → pickling → surperficial epithelium processing → drawing → oil tempering
(c) annealing → pickling → surperficial epithelium processing → mill skin (SV) → LP → pickling → surperficial epithelium processing → drawing → oil quenching
As described later shown in the embodiment, according to the present invention, for obtain Δ Cr be suppressed very low rolled wire, and adopt any one method from above-mentioned spring operation (a) to (c), also can access the extremely spring of excellence of surface texture.In addition, in order also controlling the thickness of the grain boundary oxidation layer in the rolled wire very thin, and to adopt the above-mentioned operation of spring arbitrarily, also to access the spring of excellent in fatigue characteristics.Also have, even the thickness of the grain boundary oxidation layer of rolled wire breaks away from preferable range of the present invention, if the mill skin that carries out as above-mentioned spring operation (c) is handled, because the grain boundary oxidation layer attenuation after the spring processing can access good fatigue characteristic according to experimental verification.
Be not particularly limited from each treatment process of above-mentioned spring operation (a) to (c) record, can suitably select the method for being implemented usually.For example, cleanup acid treatment, representational with good grounds following and carry out, impregnated in 5～25% H 60 ℃～90 ℃ temperature
2SO
4In, perhaps in 20 ℃～50 ℃ temperature impregnated in 5～15% HCl.
[embodiment]
Below, according to embodiment in detail the present invention is described in detail.But following embodiment does not limit the present invention, and the scope of aim described later is carried out suitable change before not breaking away from, and all is contained in the technical scope of the present invention.
(manufacturing of steel wire material for spring)
(steel grade A～G all is the examples that satisfy composition in the steel of the present invention regulation, and surplus is iron and unavoidable impurities with the various steel 150kg shown in the table 1.) with the melting of small size vacuum smelting furnace, after forge hot becomes the briquet on 155cm limit,, make the steel wire material in diameter 7.4mm footpath according to the heating hot-rolled condition shown in following from wire rod operation 1 to 3.In above-mentioned wire rod operation, wire rod operation 1 and 2 is the examples of the present invention of creating conditions that satisfy the present invention's regulation fully, and wire rod operation 3 is the both sides of Heating temperature and soaking temperature comparative examples higher than scope of the present invention.
(wire rod operation 1)
After being heated to about 1000 ℃ with 15 ℃/minute rate of heating, with about 1060 ℃ of soaking 20 minutes, at 100kgf/mm
2(
Carry out high hydraulic pressure shower under hydraulic pressure 981MPa) about 5 seconds, and implemented the deoxygenated skin.Then, carry out roughing system after, Yi Bian carry out the shower cooling of 150t/hr, on one side after carrying out finish rolling system (950 ℃ of finish rolling system temperature), after the end of finish rolling system, cool off with the speed of cooling of 6 ℃/sec and approximately to reach 700 ℃ scope.The coiling temperature is 875 ℃.
(wire rod operation 2)
After being heated to about 980 ℃ with 20 ℃/minute rate of heating, with about 1100 ℃ of soaking 30 minutes, at 100kgf/mm
2(
Carry out high hydraulic pressure shower under hydraulic pressure 981MPa) about 5 seconds, and implemented the deoxygenated skin.Then, carry out roughing system after, Yi Bian carry out the shower cooling of 150t/hr, on one side after carrying out finish rolling system (980 ℃ of finish rolling system temperature), after the end of finish rolling system, cool off with the speed of cooling of 6 ℃/sec and approximately to reach 700 ℃ scope.The coiling temperature is 875 ℃.
(wire rod operation 3)
After being heated to about 1100 ℃ with 18 ℃/minute rate of heating, with about 1300 ℃ of soaking 40 minutes, at 100kgf/mm
2(
Carry out high hydraulic pressure shower under hydraulic pressure 981MPa) about 5 seconds, and implemented the deoxygenated skin.Then, carry out roughing system after, Yi Bian carry out the shower cooling of 150t/hr, on one side after carrying out finish rolling system (1050 ℃ of finish rolling system temperature), after the end of finish rolling system, cool off with the speed of cooling of 4 ℃/sec and approximately to reach 700 ℃ scope.The coiling temperature is 875 ℃.
In each steel that so obtains, measure Δ Cr according to aforesaid method, and estimate pickling.
(evaluation of pickling)
Above-mentioned steel wire material is cut into 100mm length, and sample number (n) is 3, implements following pickling test (beaker test).Here, with actually operating in cleanup acid treatment be to experimentize under the same condition.
Pickle solution: 15% sulfuric acid
Prevent to use that as 0.5% iron branch, divalent iron is 20g/L with inhibiter (inhibitor) (cationic amine derivative cationic amine derivative) as ferritic dissolving
Immersion condition: 60 ℃, 10 minutes
Next, the oxide skin of measuring as follows after the pickling is peeled off rate.In the present embodiment, be the oxide skin adhesive rate (A described later) with respect to originally, the per-cent (B/A * 100 (%)) that the oxide skin when carrying out pickling is peeled off rate (B) defines " oxide skin after the pickling is peeled off rate ".
(1)A(％)＝[(W
0-W
1)/W
0]×100
In the formula,
The A meaning is an oxide skin adhesive rate (the oxide skin adhesive rate of steel wire material) originally
W
0The meaning is the weight (g) of the steel wire material (rolling state, be attached with oxide skin) before the dipping
W
1The meaning is the weight (g) with the steel wire material behind the above-mentioned immersion condition dipping
(2)B(％)＝[(W
01-W
2)/W
01]
The B meaning is that the oxide skin after under these conditions the pickling is peeled off rate,
W
01The meaning is the weight (g) of the steel wire material (rolling state) before the dipping
W
2The meaning is the weight (g) after the pickling experiment.
In following formula (1) and (2), W
0And W
01The meaning all is the weight of steel wire material of rolling state, still, for clear and definite " weight of each sample (rolling state steel wire material) made from the same terms ", and adopts different marks.Use same sample, can not measure above-mentioned A and B.
In the present invention, as above-mentioned and oxide skin that measure peel off rate be 100% be judged to be pickling excellence (qualified, zero).
In addition, the thickness of oxide skin, internal layer oxide skin and grain boundary oxidation layer, the composition of oxide skin is measured as follows in addition.When measuring them, above-mentioned steel wire material is imbedded resin, to after carrying out mirror ultrafinish perpendicular to the cross section (mensuration face) of rolling direction,, adopt osmium (osmium) to carry out evaporation with abrasive in order to keep electroconductibility, with it as for the use of examination material.
(thickness of oxide skin)
Adopt Fe-SEM device (the S-4500 electric field radioactive scanning electron microscope of Hitachi's system), observe above-mentioned cross section for the examination material, according to photo (multiplying power: 3000 times), the thickness of mensuration oxide skin, with its maximum ga(u)ge as " thickness of oxide skin ".
In the present invention, the thickness of the oxide skin of measuring in the above described manner be 40 μ m following be judged to be qualified.
(composition of oxide skin)
For above-mentioned cross section for the examination material, carry out the X-ray diffraction analysis of following condition, measure the composition (volumetric ratio) of oxide skin.
Device: electric system of science " RAD-RU300 "
Target: Cr
Target output rating: 40kV-200mA
Monochromator (monochromator) is subjected to optical slits (slit): 0.6mm
Slit: disperse 1 °, 1 ° of scattering is subjected to light 0.15mm
Scan speed: 2 °/minute
Measurement range (2 θ): 15 ° or 110 °
Sampling amplitude: 0.02 °/step
(thickness of internal layer oxide skin)
The same with aforementioned " thickness of oxide skin ", based on the Fe-SEM photo, measure the thickness of internal layer oxide skin, with its maximum ga(u)ge as " internal layer scale thickness ".In the Fe-SEM photo, because internal layer oxide skin is observed than oxide skin black (with reference to aforesaid Fig. 1), so both can be according to the deep or light difference of color.
In the present invention, as the thickness of the internal layer oxide skin of above-mentioned mensuration be below the 2 μ m be judged to be qualified.
(thickness of grain boundary oxidation layer)
For above-mentioned cross section for the examination material, adopt opticmicroscope (400 times of multiplying powers) to measure the grain boundary oxidation layer, with its full depth as " thickness of grain boundary oxidation layer ".
In the present invention, as above-mentioned the degree of depth of the grain boundary oxidation layer of mensuration be below the 10 μ m be judged to be qualified.
(manufacturing of spring steel wire)
Then, adopt each above-mentioned steel wire material, carry out the every of the spring operation from (a) to (c) shown in following, make the spring steel wire (oil temper wire) of diameter 4.0mm thus.In following operation, drawing, patenting (LP) and mill skin (SV) are all implemented with identical condition.
(a) surperficial epithelium processing → drawing (dry wire drawing) → oil tempering (Heating temperature: 930 ℃, the quenching oil temperature: 70 ℃, tempering temperature: 450 ℃, the cooling after the tempering: water-cooled)
(b) LP is with 930 ℃ of heating → in 600 ℃ of maintenance → pickling → surperficial epithelium processing → drawing → oil tempering
(c) annealing (keeping 2 hours) → pickling → SV → LP → pickling → drawing → oil tempering at 660 ℃
(degree of depth of grain boundary oxidation layer)
Adopt the oil temper wire that so obtains, with the above-mentioned degree of depth of measuring the grain boundary oxidation layer.In the present invention, the degree of depth of grain boundary oxidation layer be 10 μ m following be judged to be qualified.
(fatigue lifetime (resistance to cracking))
Above-mentioned oil temper wire is cut off the sample (being about 650mm) that forms prepare 50, village's formula rotary bending fatigue test in supplying.Specifically, under 45% bearing strength test of the tensile strength of each sample, carry out fatigue test (10,000 ten thousand times), measure the number of losing generation.Calculate the ratio of the generation lost (damage rate) is arranged in 50 samples.
In the present invention, be to be judged to be excellent in fatigue characteristics (qualified, zero) below 5% as above-mentioned and damage rate that measure.
Table 2 and table 3 show these results.
[table 1]
| Steel grade | C | Si | Mn | Cr | Ni | P | S | V | Ti | Nb |
| A | 0.36 | 1.42 | 0.14 | 0.51 | - | 0.020 | 0.020 | - | - | - |
| B | 0.54 | 1.51 | 0.71 | 0.70 | - | 0.018 | 0.019 | - | - | - |
| C | 0.60 | 1.58 | 0.52 | 0.56 | - | 0.010 | 0.013 | 0.160 | - | - |
| D | 0.58 | 1.54 | 0.72 | 0.92 | 0.33 | 0.005 | 0.004 | 0.080 | - | - |
| E | 0.61 | 2.05 | 0.95 | 1.02 | 0.26 | 0.006 | 0.003 | 0.105 | - | - |
| F | 0.61 | 2.12 | 0.88 | 1.85 | 0.72 | 0.013 | 0.009 | 0.33 | - | 0.050 |
| G | 0.64 | 2.45 | 0.75 | 1.12 | 0.66 | 0.014 | 0.007 | 0.25 | 0.080 | - |
[table 2]
| No. | Steel grade | Mark | Cr concentration | Scale thickness (μ m) | Internal layer scale thickness (μ m) | Oxide skin is peeled off rate [%] | The pickling sex determination | ||
| Top layer (%) | In the steel (%) | ΔCr (％) | |||||||
| 1 | A | A-1 | 0.89 | 0.51 | 0.38 | 31 | 1.6 | 100 | ○ |
| 2 | A | A-2 | 0.95 | 0.51 | 0.44 | 30 | 1.5 | 100 | ○ |
| 3 | A | A-3 | 2.15 | 0.51 | 1.64 | 32 | 0.8 | 97 | × |
| 4 | B | B-1 | 0.88 | 0.70 | 0.18 | 32 | 1.6 | 100 | ○ |
| 5 | B | B-2 | 0.75 | 0.70 | 0.05 | 22 | 1.2 | 100 | ○ |
| 6 | B | B-3 | 2.24 | 0.70 | 1.54 | 18 | 1.3 | 93 | × |
| 7 | C | C-1 | 0.68 | 0.56 | 0.12 | 19 | 1.8 | 100 | ○ |
| 8 | C | C-2 | 1.78 | 0.56 | 1.22 | 36 | 1.9 | 100 | ○ |
| 9 | C | C-3 | 2.24 | 0.56 | 1.68 | 21 | 1.0 | 95 | × |
| 10 | D | D-1 | 0.99 | 0.92 | 0.07 | 33 | 1.5 | 100 | ○ |
| 11 | D | D-2 | 2.80 | 0.92 | 1.88 | 36 | 1.6 | 90 | × |
| 12 | E | E-1 | 1.32 | 1.02 | 0.30 | 38 | 0.5 | 100 | ○ |
| 13 | E | E-2 | 2.65 | 1.02 | 1.63 | 35 | 0.6 | 90 | × |
| 14 | F | F-1 | 2.41 | 1.85 | 0.56 | 33 | 1.2 | 100 | ○ |
| 15 | G | G-1 | 1.55 | 1.12 | 0.43 | 21 | 1.6 | 100 | ○ |
[table 3]
*A: chlorohydric acid pickling → drawing → Q-tempering
B: patenting → chlorohydric acid pickling → drawing → Q-tempering
In table 2 and table 3, for example, " A-1 " meaning is to use the steel grade A shown in the table 1, by the example of wire rod operation 1 manufacturing steel wire material, A-2 " looking like is to use the steel grade A shown in the table 1, makes the example of steel wire materials by wire rod operation 2.Other example too.Also have, in table 3, gathered the kind of the spring operation when making oil temper wire.For example, in table 2 and table 3, No.1 is to use steel grade A, behind wire rod operation 1 manufacturing steel wire material, makes the example of oil temper wire by spring operation (a).Other example too.
Follow according to table 2 and table 3 and can do following investigation.
At first, No.1～2,4～5,7～8,10,12,14～15 are that Δ Cr satisfies scope of the present invention, and the thickness of oxide skin and internal layer oxide skin satisfies the example of the present invention of preferable range of the present invention, these are as shown in table 2, and it is 100% that oxide skin is peeled off rate, and pickling is extremely excellent.In addition, when investigating the oxide skin composition of above-mentioned wire rod, confirm that it all is controlled in the aforesaid preferable range (not showing) in table according to X-ray diffraction method.
In addition, in the oil temper wire that obtains at above-mentioned wire rod and the wire rod stated in the use, the generation to the grain boundary oxidation layer all unconfirmed fully, excellent in fatigue characteristics.In addition, when measuring the tensile strength of above-mentioned oil temper wire, confirm that it all has the above high strength (not showing) of about 1900～2100MPa in table according to JIS Z 2241.
Among the invention described above example, No.1～2,4～5,7～8 are by spring operation (a), No.10,12,14 and 15 is examples of making oil temper wire by spring operation (b) respectively, but,, can both obtain the spring of excellent in fatigue characteristics no matter according to which kind of method.Also have, though do not show in the table, make oil temper wire by spring operation (c), also can access the spring of excellent in fatigue characteristics, this is identified by experiment.
With respect to this, No.3,6,9,11,13 all is comparative examples, and its wire rod operation 3 that adopts Heating temperature and soaking temperature to depart from the scope of the present invention is made spring, because Δ Cr departs from the scope of the present invention, reduces (with reference to table 2) so oxide skin is peeled off rate.In addition, use above-mentioned comparative example and the steel wire material that obtains and the grain boundary oxidation layer concentration of spring all break away from preferable range of the present invention, the fatigue characteristic of spring also reduce.
Also have, as above-mentioned comparative example, the grain boundary oxidation layer depth of steel wire material departs from the scope of the present invention, if grinding skin in the mode of aforesaid spring operation (c) handles, can confirm also by experiment that then the grain boundary oxidation layer attenuation after the spring processing can access excellent fatigue characteristic.
Claims (4)
1. steel wire material for spring, it is the hot rolling wire of the surface before the pickling with oxide skin, it is characterized in that, in quality %, contain: C:0.35～0.7%, Si:1.4～2.5%, Mn:0.05～1.0%, Cr:0.5～1.9%, P:0.02% are following and do not contain 0%, and S:0.02% following and do not contain 0%, surplus is Fe
The Cr concentration on top layer and the difference of the Cr concentration in the steel is below 1.5%,
Wherein, " skin section " place when in EPMA line quantitative analysis figure the X ray intensity of Fe being reached maximum value is during as the ferrite interface, and to the zone at described interface, " the Cr concentration on top layer " be the maximum value that the Cr in this skin section measures from the surface.
2. steel wire material for spring, it is the hot rolling wire of the surface before the pickling with oxide skin, it is characterized in that, in quality %, contain: C:0.35～0.7%, Si:14～2.5%, Mn:0.05～1.0%, Cr:0.5～1.9%, P:0.02% are following and do not contain 0%, and S:0.02% following and do not contain 0%
The Cr concentration on top layer and the difference of the Cr concentration in the steel is below 1.5%,
Wherein, " skin section " place when in EPMA line quantitative analysis figure the X ray intensity of Fe being reached maximum value is during as the ferrite interface, and to the zone at described interface, " the Cr concentration on top layer " be the maximum value that the Cr in this skin section measures from the surface,
In quality %, also contain from the group of following formation, select at least a:
V:0.07～0.4%, Ti:0.01～0.1% and Nb:0.01～0.1%,
Surplus is Fe.
3. steel wire material for spring, it is the hot rolling wire of the surface before the pickling with oxide skin, it is characterized in that, in quality %, contain: C:0.35～0.7%, Si:1.4～2.5%, Mn:0.05～1.0%, Cr:0.5～1.9%, P:0.02% are following and do not contain 0%, and S:0.02% following and do not contain 0%
Also contain Ni:0.15～0.8%,
Surplus is Fe,
The Cr concentration on top layer and the difference of the Cr concentration in the steel is below 1.5%,
Wherein, " skin section " place when in EPMA line quantitative analysis figure the X ray intensity of Fe being reached maximum value is during as the ferrite interface, and to the zone at described interface, " the Cr concentration on top layer " be the maximum value that the Cr in this skin section measures from the surface.
4. a spring is characterized in that, adopts the described steel wire material for spring of claim 1 to make.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005334846 | 2005-11-18 | ||
| JP2005-334846 | 2005-11-18 | ||
| JP2005334846A JP4369416B2 (en) | 2005-11-18 | 2005-11-18 | Spring steel wire rod with excellent pickling performance |
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| Publication Number | Publication Date |
|---|---|
| CN1966755A CN1966755A (en) | 2007-05-23 |
| CN1966755B true CN1966755B (en) | 2011-04-13 |
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| CN2006101603482A Expired - Fee Related CN1966755B (en) | 2005-11-18 | 2006-11-15 | Steel wire material for spring with excellent acid rinsing property |
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|---|---|
| JP (1) | JP4369416B2 (en) |
| KR (1) | KR100823780B1 (en) |
| CN (1) | CN1966755B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5624503B2 (en) * | 2011-03-04 | 2014-11-12 | 日本発條株式会社 | Spring and manufacturing method thereof |
| JP5824443B2 (en) * | 2012-11-22 | 2015-11-25 | 株式会社神戸製鋼所 | Method of manufacturing steel wire for spring |
| JP6085192B2 (en) * | 2013-03-01 | 2017-02-22 | 株式会社神戸製鋼所 | Steel wire for springs excellent in drawability and manufacturing method thereof |
| CN104451441A (en) * | 2014-11-08 | 2015-03-25 | 江苏天舜金属材料集团有限公司 | Prestressed wire for bridge and production process of prestressed wire |
| CN105648318A (en) * | 2016-02-25 | 2016-06-08 | 邢台钢铁有限责任公司 | Refined wire with high low-temperature high-speed torsional property and production method and application thereof |
| CN105734415A (en) * | 2016-02-26 | 2016-07-06 | 邢台钢铁有限责任公司 | Refined wire with high torsion performance and preparation method and purpose thereof |
| JP2017179423A (en) * | 2016-03-29 | 2017-10-05 | 株式会社神戸製鋼所 | Steel wire with excellent fatigue characteristics, and method for producing the same |
| CN107557672A (en) * | 2017-10-30 | 2018-01-09 | 太湖县爱杰机械铸造有限公司 | A kind of automobile hanging spring steel and preparation method thereof |
| CN108179355A (en) * | 2018-01-31 | 2018-06-19 | 中钢集团郑州金属制品研究院有限公司 | A kind of high-intensity and high-tenacity spring steel wire and its preparation process |
| US20220251693A1 (en) * | 2019-07-10 | 2022-08-11 | Nippon Steel Corporation | Hot rolled steel sheet |
| CN111237366B (en) * | 2020-03-19 | 2022-02-11 | 毕克礼斯精密部件（太仓）有限公司 | Variable-pitch arc spring |
| JP7428889B2 (en) | 2020-03-27 | 2024-02-07 | 日本製鉄株式会社 | steel material |
| WO2024101377A1 (en) * | 2022-11-08 | 2024-05-16 | 日本発條株式会社 | Steel wire material and method for manufacturing steel wire material |
| WO2024101376A1 (en) * | 2022-11-08 | 2024-05-16 | 日本発條株式会社 | Steel wire rod and manufacturing method for steel wire rod |
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| JPH06299295A (en) * | 1993-04-13 | 1994-10-25 | Kobe Steel Ltd | Steel for high strength spring and its production |
| KR100514120B1 (en) * | 2000-12-20 | 2005-09-13 | 신닛뽄세이테쯔 카부시키카이샤 | High-strength spring steel and spring steel wire |
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| CN1966755A (en) | 2007-05-23 |
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| KR100823780B1 (en) | 2008-04-21 |
| JP2007138260A (en) | 2007-06-07 |
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